The troops, many badly injured, got safe passage from the battered plant after heroically stalling the invaders' advance.
Now they are in Moscow's hands amid fears about their fate after death threats.
The brave marines had been holed up in tunnels below the Azovstal steelworks, fending off repeated attacks, in the vital port city for more than three months.
Hundreds more remain beneath the plant – many injured – the Ukraine military said. Negotiations would continue to ensure their safe release but the "combat mission” was over, military chiefs added.
Ukraine's Deputy Defence Minister Hanna Maliar said 53 badly-wounded soldiers were taken to Novoazovsk, a town held by Russian-backed rebels. She said another 211 were evacuated using a humanitarian corridor to Olenivka another Moscow-held town near Donetsk.
The Kremlin earlier confirmed a deal had been reached to evacuate the injured troops in exchange for captured Russian soldiers. However, Russian spokesman Dmitry Peskov then declined to say whether the Ukrainian soldiers would be treated as war criminals or as prisoners of war.
He said: "Putin has guaranteed that they will be treated in line with the relevant international laws."
In the Russian parliament, Speaker Vyacheslav Volodin said those evacuated should not be subject to exchange.
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