Team GB did not enter a women's team into the last Olympics in 2016 due to disagreements between the four home nations, and this year's tournament is Chile's first appearance at the Olympic Games.
Great Britain's head coach Hege Riise, who won Olympic gold as a player with her native Norway in 2000, was appointed GB's manager in March, and is also England's interim boss.
The squad qualified for the Tokyo Olympics via England's run in the 2019 World Cup, when they reached the semi-final stage in France.
GB's only appearance in an Olympics to date was when they hosted the tournament in 2012; despite qualifying for the 2008 summer games they did not enter a team as the Scottish, Welsh, Northern Irish and English Football Associations failed to reach an agreement.
During the tournament nine years ago, the GB women's team won all three of their group stage games against Brazil, New Zealand and Cameroon.
However, progressing from the quarter-final stage proved to be a step too far as the side fell to a 2-0 defeat at the hands of Canada, who went on to finish third in 2012.
Chile's rise in women's football started five years ago after the nation dropped out of FIFA's world rankings due to inactivity, and now they sit 37th and are among the top 40 teams in the world for the first time.
They finished as runners-up in the 2018 Copa America and qualified for their first World Cup a year later, when they could not manage progression from the group stages in France.
Lyon's goalkeeper Christiane Endler is the standout player for Chile, after helping Paris Saint-Germain win their first French league title last season and she has over 100 appearances for club and country.
Jose Letelier is the manager of Chile's women's squad for this year's Olympics, and he has been the national side's head coach since 2015.
Unlike the men's squads at the Olympics, the women's teams have no age cap on its players, meaning that the tournament is recognised as highly as the World Cup by FIFA.
The GB squad is predominantly made up from England internationals, with only Wales' Ingle and Scotland duo Little and Caroline Weir representing their home nations, meaning that it is likely Riise will opt for a similar formation to the one she used with England in international friendlies in April.
Le Havre midfielder Francisca Lara is Chile Women's all-time top goalscorer, netting 21 times in 59 appearances for her country, and she is expected to start on Wednesday.
Great Britain Women possible starting lineup:
Roebuck; Stokes, Houghton, Bright, Bronze; Ingle, Little; Hemp, Stanway, Kirby; White
Chile Women possible starting lineup:
Endler; Toro, Guerrero, Pardo, Lopez; Lara, Araya, Lopez, Zamora; Aedo, Urrutia
We say: Great Britain Women 2-0 Chile Women
GB will need to get off to a winning start on Wednesday against the lowest-ranked side in Group E, as clashes with Canada and hosts Japan are to follow.
There are enough players in the GB squad who competed in 2012 and gained experience of an Olympics tournament that they should use to beat Chile on Wednesday, when Letelier's squad could be overwhelmed by the experience of their first Olympic Games.