Ukraine’s Government received 76 captives, with the pro-Russian separatists reportedly taking 124. Volodymyr Zelensky met them in the airport.
Russian and Ukrainian authorities agreed to the swap - which is aimed at improving ties - at talks in December.
Relations between the two countries deteriorated in 2014, when Russia annexed Ukraine"s Crimean peninsula.
Russian-backed rebels then began an insurgency in the Donetsk and Luhansk regions of eastern Ukraine. More than 13,000 people have been killed in the conflict.
According to Zelensky, a total of 81 Ukranians had been released.