"There will be an ambassador of Syria in France," Hollande announced. France expelled its Syrian ambassador in May, along with more a half-dozen other countries.
Mouaz Al-Khatib, the opposition leader, described Makhous as "one of the first to speak of liberty" in Syria. He holds four doctorate degrees and belongs to the Muslim Alawite sect of President Bashar al-Assad, demonstrating an effort to reach out to all of Syria's people, Khatib said.
France recognized the coalition days after it was formed last Sunday - and so far is the only Western country to do so.
France also took the lead in backing the Libyan opposition that ultimately ousted leader Moammar Gadhafi, and flew the first mission of the international coalition providing air support to Libyan rebels.
There is widespread fear that without a legitimate opposition force the civil war in Syria could degenerate into sectarian battles pitting community upon community.
But, the United States and other EU nations have said they prefer to wait and see whether the coalition truly represents the variety of people that make up Syria before they recognize it.
Khatib suggested that a provisional government made up of technocrats would come quickly, a move that would allow the ambassador to take up his functions. A military command is also being formed and a coordination center devoted to humanitarian aid will be set up in Cairo.
"I say frankly that we have no hidden agenda. There are no hidden accords, no hidden decisions were made," Khatib said in a bid to reassure other nations.
"Our role will end as soon as this regime falls. The Syrian people can then decide in all freedom the democratic institutions, the form of constitutional regime that they want," he said. "The people can take their decisions freely."
A Syrian government official dismissed Makhous' appointment, saying it was made at the behest of France. "If France has appointed him, then he is a French ambassador, not a Syrian one," he said.
The official spoke to the Associated Press on condition of anonymity because he was not authorized to comment publicly on the subject.
More than 36,000 people have been killed since the Syrian uprising against President Bashar Assad began in March 2011 and the new coalition is pressing for the means to defend Syrian civilians.
On Saturday, Syrian rebels took control of the Hamdan airport in the oil-rich province of Deir el-Zour along the border with Iraq after days of heavy fighting with Assad's forces, Rami Abdul-Rahman, the chief of the Britain-based Syrian Observatory for Human Rights, said.