The first batch of Indian nationals from Ukraine reached Romania on Friday afternoon after crossing the Suceava border post, the ministry of external affairs said.
Officials said more Indians in small groups are expected to reach Romania through the border crossing.
"The first batch of evacuees from Ukraine reach Romania via Suceava border crossing. Our team at Suceava will now facilitate travel to Bucharest for their onward journey to India," MEA spokesperson Arindam Bagchi said.
In a tweet, he also shared visuals of the Indians transiting the border post.
Senior officials said Air India will operate two flights to the Romanian capital Bucharest on Friday to evacuate the Indians. More flights are likely to operate over the next few days.
The two Air India flights are expected to depart Bucharest on Saturday.
India is trying to evacuate its nationals through Ukraine's land borders with Hungary, Poland, Slovakia after the Ukrainian government closed the country's airspace following the Russian military offensive.
Earlier, the Indian embassy in Ukraine said over 470 students will exit Ukraine and enter Romania through the Porubne-Siret border on Friday and that it is moving them to neighbouring countries for onward evacuation.
It said that the "massive evacuation" operation was organised through the joint efforts of Indian embassies in Ukraine, Poland, Romania and Hungary and that efforts are underway to relocate Indians coming in from the hinterland.
As India stepped up efforts to evacuate around 16,000 of its citizens, mostly students, External Affairs Minister S Jaishankar, during a phone conversation with Ukrainian Foreign Minister Dmytro Kuleba, discussed the predicament of the Indian nationals and appreciated his support for their safe return.
"Received call from Ukrainian FM @DmytroKuleba. He shared his assessment of the current situation.I emphasised that India supports diplomacy & dialogue as the way out," Jaishankar tweeted.
"Discussed predicament of Indian nationals, including students. Appreciate his support for their safe return," he added.