[3] The remaining eight athletes on the Moldovan squad had past Olympic experience, highlighted by hammer thrower Serghei Marghiev and his older sisters Zalina Marghieva and Marina Nichișenco, shot putter Ivan Emilianov, who qualified for his fourth Games as the oldest and most experienced competitor (aged 39), taekwondo fighter Aaron Cook, who transferred his allegiance from Great Britain after controversially failing to make the London Games in 2012, and freestyle wrestler Nicolae Ceban, who reprised his role of leading the Moldovan team for the second time as the flag bearer in the opening ceremony.

[10] Meanwhile, the men's C-2 1000 m crew added their boat to the Moldovan team for the Games, as the International Canoe Federation had decided to revoke its license from Romania due to the canoeists' doping violations at the European Championships.

Valeriu Duminică earned a continental quota spot from the European region, as Moldova's top-ranked judoka outside of direct qualifying position in the IJF World Ranking List of 30 May 2016.

[19] Meanwhile, an unused women's Olympic spot was awarded to the Moldovan team by IWF, as a result of Russia's complete ban from the Games due to the "multiple positive cases" of doping.

[21] On 11 May 2016, United World Wrestling awarded an additional Olympic license to Moldova in women's freestyle 58 kg, as a response to the doping violations on the Ukrainian wrestler at the European Qualification Tournament.