Hollande said the coalition was a "decisive step towards the creation of a new Syria" and urged Mouaz Alkhatib to do his utmost to prepare it for government, a statement issued by Hollande's office said.
France was the first European power to recognize the coalition, agreed on Sunday, as the sole representative of its people.
Hollande spoke to Alkhatib by telephone and urged him to "do all he can to consolidate the coalition's authority and credibility inside Syria and move rapidly towards establishment of a provisional government", the statement said.
Foreign Minister Laurent Fabius said Alkhatib was expected in Paris within days.
Alkhatib is a moderate Sunni Muslim cleric who fled to Cairo in July after repeated detentions by Syrian secret police.
The 52-year-old is seeking international recognition for a transitional government as a precursor to acquiring weapons from abroad.
France is one of the harshest critics of Syrian President Bashar al-Assad, who has vowed to fight to the death in a conflict that has already killed an estimated 38,000 people and risks sucking in other countries.