Khalid Khoja was elected president in a close vote late yesterday during a three-day meeting in Istanbul of the National Coalition.
The coalition is seen as separate from the military opposition fighting President Bashar al Assad but it is involved in talks with international negotiators looking for ways to end the civil war that has left more than 200,000 dead.
Khoja replaces Hadi al Bahra, who did not run for re-election.
The meeting comes amid a push by Russia, a key supporter of Assad, to try to bring the Syrian government and the opposition together in Moscow for talks.
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In the next stage, they would be joined by Syrian government representatives.
At a press conference today, Khoja said Russia has invited some members of the National Coalition to the talks but not the whole group. As such, he said no one from the coalition is prepared to go.
Another issue is that Khoja does not see Russia as a neutral broker.
"Moscow is one of the enemies of the Syrian revolution," he said.