La Roja have triumphed in the last two editions of the tournament, picking up the trophy on home soil in 2015 and again 12 months later in the United States.
Chile collected six points from their three Group C matches to make the quarter-finals, following wins over Japan and Ecuador with a defeat to Uruguay.
The holders have only lost two of their last 15 Copa America matches and have won seven of their 11 matches against Colombia at the competition.
Here, Sports Mole takes a look at how Reinaldo Rueda's team could line up when they take to the field for Friday's affair in Sao Paulo.
Chile's main injury concern ahead of the match concerns Gary Medel, who had to be replaced in the 55th minute of the clash with Uruguay last time out. Medel is seen as a huge doubt, which gives Rueda a selection issue.
A return to a back four would likely see the experienced Gonzalo Jara line up alongside Guillermo Maripan in central defence, with Mauricio Isla and Jean Beausejour continuing in the two full-back positions.
Arturo Vidal's lack of fitness makes the Barcelona midfielder a doubt. The 32-year-old should make it, however, to line up alongside Erick Pulgar and Charles Aranguiz, who provided three assists in the group stages.