Hijab was chosen in December as general coordinator of several opposition groups which are preparing for possible talks with the government in Damascus.
"We cannot negotiate with the regime while there are foreign forces bombing the Syrian people," Hijab said after a meeting with French President Francois Hollande in Paris.
His visit to France comes two weeks ahead of proposed UN-brokered peace talks to seek an end to a conflict that has claimed more than a quarter of a million lives since it began nearly five years ago.
He called for "immediate humanitarian measures" in areas under siege, such as the rebel-held town of Madaya where at least 28 people have reportedly starved to death since December 1 under a regime blockade.
French Foreign Minister Laurent Fabius earlier called on the Syrian regime to end the siege of Madaya and said a halt to air strikes by the regime and its Russian ally was an "absolute necessity".
Deliveries of food, medicine and blankets began Monday to Madaya, the International Committee of the Red Cross said.
Russia, a staunch ally of Syrian President Bashar al-Assad, began a campaign of air strikes in support of the regime in late September.
Moscow says it is targeting the Islamic State group and other "terrorists" and has dismissed reports that its raids have killed hundreds of civilians as "absurd".
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