Bolivian Olympic Committee (Spanish: Comité Olímpico Boliviano sent the nation's second-largest delegation in history to the Games, falling short of a roster size set in Barcelona 1992 by a single athlete.

[2] Notable Bolivian athletes featured pistol shooter Rudolf Knijnenburg, who staged his comeback in Rio de Janeiro after a twelve-year absence, freestyle swimmer Karen Torrez, and race walkers Claudia Balderrama and Ángela Castro, who was chosen to lead the team as the nation's flag bearer into the opening ceremony.

[5] Bolivia has qualified one judoka for the men's middleweight category (90 kg) at the Games, signifying the nation's Olympic return to the sport for the first time since 2004.

Martin Michel earned a continental quota spot from the Pan American region as the Bolivia's top-ranked judoka outside of direct qualifying position in the IJF World Ranking List of 30 May 2016.

[6] Bolivia has received two invitations from the Tripartite Commission to send shooters competing in the men's pistol and women's rifle events to the Olympics.