It means that City’s record goal-scorer, who becomes a Barcelona player on 1 July, is still breaking records at the age of 33.
Kun is now his country’s seventh most-capped player.
Argentina’s victory means they will now face Ecuador in the quarter-finals on 3 July in Goiânia, Brazil.
Aguero, who made his international debut almost 15 years ago, has never won the Copa America having been a runner-up twice in 2015 and 2016.
Though he has reached a century of caps, only 20 of them have come in the last four years with injury plus limited selection opportunities restricting his progress.
He’s scored 41 goals in total for La Albiceleste, though reaching a century of international caps will have no doubt been high on his wish-list of achievements as he enters the later stages of a glittering career.
And with the World Cup in Qatar next year, Aguero could be targeting his international swansong on the biggest stage in world football.
Argentina eased to a third win in four Copa America matches against Bolivia, with Lionel Messi setting up Papu Gomez with a delightful chip that the Sevilla man volleyed into the roof of the net for the opener on six minutes.
Messi, earning a record 148th cap for his country, then doubled the lead himself from the penalty spot after Gomez was fouled in the box.
And the Barcelona legend scored his second and Argentina’s third after an excellent through-ball from Aguero saw him deftly flick the ball over the keeper to make it 3-0 at the break.
Erwin Saavedra pulled a goal back for Bolivia after the break and Aguero was replaced by Inter Milan’s Lautaro Martinez on 63 minutes who took just two minutes to score Argentina’s fourth of the evening in Cuiaba.
Everyone at Manchester City would like to congratulate Sergio on reaching this fantastic international milestone