The flight operated by Vietnam Airlines departed Hanoi to go to Bucharest, Romania on Monday.
It will be the first to repatriate Vietnamese people from Ukraine, following a government plan that was announced last week.
Set to land in Hanoi within Tuesday, the flight will bring home 85 children under 12 among the passengers, according to the Vietnam News Agency.
As of 6 p.m. Monday, 2,200 Vietnamese had been evacuated from Ukraine and arrived in Poland, according to the Ministry of Foreign Affairs. 830 others have arrived in Romania, 310 in Hungary, 100 in Slovakia and 20 in Russia, it added.
"Everybody seems brighter today. We’ve have done everything we could to support them," said Pham Duy Hung, deputy head of the Vietnamese Association in Romania.
The second repatriation flight from Bucharest has been scheduled for Thursday.
Before conflicts between Ukraine and Russia broke out, there were around 7,000 Vietnamese living in Ukraine, mostly in major cities like Kyiv (around 800 people), Kharkiv (around 3,000) and Odessa (around 3,000).
Russia on Feb. 24 started authorizing what it calls a "special military operation" on Ukraine.
In a phone call with Turkish President Tayyip Erdogan, Putin said he was ready for dialogue to end the fighting but that any attempt to draw out talks would fail, according to the Kremlin, according to Reuters.
The suspension of the operation, "is only possible if Kyiv stops military operations and carries out well-known Russian demands," the Kremlin said.