The Romanian Interior Ministry confirmed 93 people would arrive back in the country on two flights.
Criticism mounted Wednesday of France's move to expel the minority group, with Romania warning of a xenophobic reaction and the EU calling on France to obey migration rules.
Romanian Foreign Minister Teodor Baconschi told RFI the French policy was cause for concern.
"I am worried about the risks of populism and xenophobic reactions in a context of economic crisis", Baconschi said.
The first group of 93 Roma agreed to a so-called "voluntary return procedure". They will be flown to Bucharest and will be granted 300 euros for adults and 100 euros for minors.
The European Union's executive arm said Wednesday that France must abide by the bloc's freedom of movement rules when it expels Roma living illegally in the country.
Most of the Roma who were sent to Romania last year returned to France afterwards as European citizens.
The French foreign ministry insisted that the measures being taken against the Roma were in line with European rules.
Foreign ministry spokesman Bernard Valero said a European directive "expressly allows for restrictions on the right to move freely for reasons of public order, public security and public health".
Krassimir Kanev, head of rights watchdog the Helsinki Committee in Bulgaria, said he was "worried by the measure aimed at an ethnic group".
Human rights groups and media in Bulgaria also criticised France's handling of the Roma question, though the foreign ministry in Sofia said it did not expect many Bulgarians to be affected.
There are about 15,000 gipsies and Roma of Eastern European origin in France.
The Roma community in Romania numbers 530,000, according to the national census, or 2.5 million according to non-governmental organisations, who say that some do not declare themselves as Roma fearing discrimination.