The South Americans go into this summer's tournament with high hopes despite a tough group, having impressed against the likes of Brazil, Spain and England over the past year, with some tipping them as dark horses to reach the final four.
Such a performance would rival their previous best showing in the competition, when they finished third in the 1962 tournament that they also hosted.
Here, to continue our countdown to the World Cup, Sports Mole looks at the top 10 players in the history of La Roja.
10. Arturo Vidal (2007-present, 53 caps, eight goals)
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Since his move to Europe from Colo Colo in 2007, Arturo Vidal has established himself as one of the continent's finest box-to-box midfielders. The 26-year-old has plenty of time to work his way up this list in the coming years having already made 53 appearances in a seven-year international career.
A staple of the Juventus midfield since joining the club in 2011, Vidal has helped the Italian giants to two Serie A titles, including an unbeaten 2011-12 campaign, while they are well on their way to a third triumph in the 2013-14 season.
He was named as the club's Player of the Year for his performances in the 2012-13 title-winning campaign, while he was also voted the Chilean Player of the Year in 2010.
9. Sergio Livingstone (1941-54, 52 caps, no goals)
Sergio Livingstone became Chilean football's first real star throughout the 1940s and into the 1950s, bursting onto the scene with a string of impressive displays in the 1941 South American Championships that earned him the Player of the Tournament award.
He went on to make a record 34 appearances in that competition, now known as the Copa America, while he also featured for his country in the 1950 World Cup, although Chile were unable to get past the first group phase in Brazil.
Nicknamed 'The Toad' due to his stance while standing in goal, Livingstone retired as the most capped player in Chile's history having also won two domestic league titles at club level.
8. Carlos Reinoso (1966-77, 34 caps, seven goals)
Despite his relatively few caps for the national side, Carlos Reinoso left an indelible mark on Chilean football with his swashbuckling displays in midfield during an 11-year international career.
His success at club level was even greater, with the bulk of his career being spent at Club America in Mexico. There, Reinoso won two league titles, the Mexican Cup, the CONCACAF Champions League and the Copa Interamericana before being voted the greatest player in the club's history.
7. Leonel Sanchez (1955-68, 84 caps, 23 goals)
With 84 appearances for La Roja, no player has represented Chile more often than Leonel Sanchez. The left-winger enjoyed a 13-year international career that spanned two World Cups, including the 1962 edition on home soil.
Sanchez finished as joint top scorer of that tournament having netted four times in just six matches and was included in the All-Star Team as Chile recorded their best-ever finish at a World Cup. He also featured four years later in England, although the team failed to get past the first round on that occasion.
He spent the majority of his club career at Universidad de Chile despite receiving offers from European giants such as AC Milan, scoring 366 goals in just 411 matches to help his side to six national championships in the space of 10 years.
6. Francisco Valdes (1962-75, 52 caps, nine goals)
Despite spending most of his career as an attacking midfielder rather than a centre-forward, Francisco Valdes had an uncanny eye for goal that led to him becoming the highest scorer in the history of the Chilean First Division.
The vast majority of his 215 domestic strikes came with Colo Colo, where he won two league titles and finished as runner-up in the 1973 Copa Libertadores. His 180 goals during two spells at the club puts him at the top of the their scoring charts and he is widely regarded to be among their greatest ever players.
At international level he featured for Chile at the 1966 and 1974 World Cups, although on both occasions La Roja failed to progress past the group stages.
5. Carlos Caszely (1969-85, 49 caps, 29 goals)
Another idol of Colo Colo, Carlos Caszely spent 11 years at the club over two spells, helping them to five league titles and second place in the 1973 Copa Libertadores. He finished as top scorer of the competition that year, a feat he also managed in three consecutive seasons in the Chilean league.
The forward was voted as the best player of the 1979 Copa America, although his two World Cup tournaments will be less fondly remembered as he became the first player to be shown a red card in the competition's history in 1974 before missing a penalty eight years later.
Off the field, Caszely made waves with his political views as he became one of the few public figures to speak up against the brutal Pinochet dictatorship in the country.
4. Alexis Sanchez (2006-present, 65 caps, 22 goals)
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The success that Alexis Sanchez has enjoyed since joining Barcelona has made him the darling of the national team, and he is expected to be their star performer in Brazil this summer having also featured for the team four years ago in South Africa.
The 25-year-old still has the best years of his career ahead of him but has already won a La Liga title, the Copa del Rey and the FIFA Club World Cup with a dominant Barcelona side. He also scored both goals for Chile as they beat England at Wembley in November last year, emulating Marcelo Salas's feat from 15 years previous.
His tally of 65 caps at such a young age points to the level of esteem he is held in in his own country, and he is well on course to become Chile's most capped player of all time.
3. Ivan Zamorano (1987-2001, 69 caps, 34 goals)
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A prolific goalscorer at both club and international level, Ivan Zamorano is the second-highest scorer in Chile's history with an impressive return of 34 goals from just 69 matches. His international career spanned 14 years and one World Cup as he started every match in France 1998.
He notably played for Spanish giants Real Madrid at club level, scoring 37 goals in 45 matches during his debut season at the Bernabeu and going on to net 77 times in 137 games overall. He also turned out for Inter Milan and Sevilla in addition to stints in Chile, Switzerland and Mexico, scoring almost 350 career goals all told.
He helped Chile to a bronze medal at the 2000 Olympic Games, finishing the tournament as top scorer, while he also picked up a La Liga title, a Copa del Rey and a UEFA Cup during his time in Europe.
2. Marcelo Salas (1994-2007, 71 caps, 37 goals)
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Alongside Zamorano up front at the 1998 World Cup was Marcelo Salas, who scored four goals in four games at that tournament and went on to become his country's highest ever goalscorer with 37 from just 71 appearances.
A prolific scoring record for both Universidad de Chile and River Plate led to a big-money move to Lazio in 1998, where he won the Serie A, the Coppa Italia and the Cup Winners' Cup in a successful three-year stint. A move to Juventus followed and, while his time there was hampered by injury, he still managed to add a further two league titles to his collection.
Having scored 11 goals in the qualifying campaign for France '98, Salas also scored twice at Wembley to hand Chile a famous victory over England before going on to net against both Italy and Brazil in the tournament itself.
1. Elias Figueroa (1966-82, 47 caps, two goals)
The undoubted king of Chilean football, Elias Figueroa is not just highly regarded in his own country but is also renowned as one of the greatest defenders in the history of the game. Indeed, Pele himself argued that he would be considered the best had he won a World Cup, while Franz Beckenbauer dubbed himself "the European Figueroa".
Captaining Chile through their most successful period as they qualified for three World Cups in 16 years, Figueroa was named the best central defender of the 1974 tournament and was included in the All-Star Team that year. He also led La Roja to a surprise runners-up place in the 1979 Copa America.
He became the first player to be named South American Footballer of the Year three times, doing so consecutively between 1974-76, while he was also named the 37th-best player and eighth-best South American of the 20th century by IFFHS.
Chile will face Spain, Netherlands and Australia in the group stages of this summer's World Cup, and you can follow every match live with Sports Mole.
Continuing our 50-day countdown to the tournament, we will be looking at the greatest players in the history of Colombia tomorrow. You can also see all of the World Cup top 10 lists so far by clicking here.