The Montenegrin team featured a number of returning Olympians; seven of them have attended in every edition of the Games since Montenegro's official debut eight years earlier, including six water polo players, led by captain Predrag Jokić, and half-middleweight judoka Srđan Mrvaljević (men's 81 kg).

Meanwhile, handball team captain Bojana Popović, who helped her fellow players deliver a historic silver-medal finish for Montenegro in London four years earlier, became the nation's first ever female athlete to carry the flag in the opening ceremony.

[1] Montenegro narrowly missed an opportunity to add another medal to its Olympic treasury in Rio de Janeiro, as the men's water polo team, led by Jokić, lost to the Italians for the bronze with a score 10–12.

[9] Head coach: Dragan Adžić Montenegro has received an invitation from the Tripartite Commission to send a judoka competing in the men's half-middleweight category (81 kg) to the Olympics.

[16][17] Key: The Montenegro men's water polo team qualified for the Olympics after securing a spot in the final and having attained an automatic berth by virtue of Serbia, as 2015 FINA World League champions, winning the other semifinal at the 2016 European Championships in Belgrade.