The move was announced by President Francois Hollande at a televised news conference in Paris.
Syrian opposition groups struck a deal in the Qatari capital Doha on Sunday to form a broad coalition to overthrow President Bashar al-Assad.
The US and Britain have both signaled support for the coalition.
But they stopped short of recognizing it as a government-in-exile.
Gulf Arab states have declared the coalition to be the sole legitimate representative of the Syrian people.
Opposition and human rights activists estimate that more than 36,000 people have been killed since the uprising against President Bashar al-Assad’s rule began in March 2011.
More than 408,000 Syrians have fled to neighboring countries, and more are fleeing every day, according to the United Nations.
Francois Hollande told reporters: “I announce today that France recognizes the Syrian National Coalition as the sole legitimate representative of the Syrian people and as the future government of a democratic Syria, allowing it to bring an end to Bashar al-Assad’s regime.”
Francois Hollande’s announcement is a clear sign that the West is now pinning its hopes on the Syrian opposition finally being able to offer a united and effective alternative to President Bashar al-Assad.
The National Coalition for Syrian Revolutionary and Opposition Forces has been calling on European nations to recognize it as the country’s transitional government, enabling it to buy weapons to assist its attempts to overthrow President Bashar al-Assad.
Fancrois Hollande said France would look at the question of arming the coalition, but that it would not support doing so “as long as it wasn’t clear where these weapons went”.
“With the coalition, as soon as it is a legitimate government of Syria, this question will be looked at by France, but also by all countries that recognize this government,” he said.
In Washington, state department deputy spokesman Mark Toner said the US regarded the National Coalition as “a legitimate representative” of the Syrian people.
“We now have a structure in place that can prepare for a political transition,” he told reporters.
“But… we’re looking for it to still establish the types of technical committees that will allow us to make sure our assistance gets to the right places.”
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