Five of the 10 top-ranked national teams in the world will take the field for the 100th anniversary edition of the South American tournament, a special event hosted by the United States starting June 3.
Top-ranked Argentina are in the 16-team tournament, which will feature stars such as Lionel Messi, Javier Hernandez, Luis Suarez and James Rodriguez.
The Hawk-Eye system was used at last year's women's World Cup in Canada and is used by UEFA, the English Premier League, German Bundesliga and Italian Serie A.
It will deploy seven cameras for each goal in all 10 stadiums to be used in the Copa America, using vibration and visual signals on each match official's watch to indicate a goal within one second of the ball crossing the goal line.
Such technology is unprecedented for South and North American events. The Copa Centenario opens June 3 when the US entertain Colombia at Santa Clara, California.
Argentina and Chile will meet in a repeat of last year's Copa America final on June 6, while Mexico and Jamaica meet in a North American rematch of last year's Gold Cup final on June 9. The final wil be staged June 26 at East Rutherford, New Jersey.
Also Wednesday, match officials from 18 North and South America nations were named for the tournament, though not appointed to specific matches.
Among the 10 South American and eight North American referees appointed was American Mark Geiger, who lost control of a Gold Cup semi-final last year between Mexico and Panama.
His decisions included a dubious early red card to Panama's Luis Tejada and a controversial handball call that gave Mexico a penalty-kick equalizer in the last minute.
Geiger needed security to exit the field and Panama coaches and players said they were "robbed" after the match.