The Belarusian team featured two defending Olympic champions: discus thrower Ellina Zvereva and single sculls rower Ekaterina Karsten.

Along with Zvereva and Karsten, shooters Sergei Martynov, Kanstantsin Lukashyk, and Igor Basinski, and married couple Iryna Yatchenko and Igor Astapkovich competed at their fourth Olympic Games, although they first appeared as part of either the Soviet Union (Martynov and Basinski in 1988) or the Unified Team (Astapkovich, Yatchenko, Lukashyk, and Karsten in 1992).

Three-time Olympic champion and wrestling coach Alexander Medved became the nation's flag bearer in the opening ceremony.

Five Belarusian athletes set the nation's historical record to win Olympic medals for the first time, including judoka Ihar Makarau in the men's half-heavyweight division, track cyclist Natallia Tsylinskaya in the women's time trial, and sprinter Yulia Nestsiarenka, who became the first non-American to claim the Olympic title in the women's 100 metres since 1980.

They competed in seven events, earning a bronze medal in the flatwater men's double kayak 500 metre race.

Three Belarusian athletes qualified to compete in the modern pentathlon event through the European and UIPM World Championships.