The captives – who include activists and journalists – were exchanged on Wednesday near the town of Horlivka, northeast of Donetsk.
Under the terms of the agreement, 74 Ukrainian soldiers were expected to be swapped for 306 pro-Russian separatists.
However, Ukraine handed over some 235 people – the others either chose to stay in Ukraine or had been released earlier, according to Ukrainian officials.
“All 74 Ukrainian hostages are already at home, on the territory controlled by our army,” Ukrainian President Petro Poroshenko wrote on Twitter.
This is the first prisoner swap in eastern Ukraine since September 2016.
In Horlivka, dozens of family members eagerly awaited the return of their loved ones.
“The first thing I’ll say to my husband is that your time in prison has not been in vain and, of course, I love you,” Natalya Gerasimenko, wife of Mykola Gerasimenko, a driver in the Ukrainian army who was detained by pro-Russian forces for almost three years, told Al Jazeera.