Combative former interior minister Nicolas Sarkozy was favourite to win after opinion surveys conducted on the eve of polling gave him a commanding 10-point lead over Segolene Royal, a regional leader and former schools minister.
Voter stations in mainland France opened across the country at 0800 am (1130 hrs IST), but about 1 million citizens in France's overseas territories and French residents in the Americas voted on Saturday in a move to encourage voter participation.
In total, 44.5 million French voters were eligible to cast their ballot. Opinion polls giving an initial indication of the result are expected to be released straight after voting ends at 0800 pm (2330 hrs IST).
Royal will need a political tsunami to sweep away her rival and win the Elysee but whoever triumphs, the election marks a generational shift as incumbent Jacques Chirac, 74, bows out after 12 years at the head of the euro zone's second economy.
Today's vote is the culmination of a fierce campaign in which Royal warned her opponent would be a ''dangerous choice'' whose election could spark suburban riots.
Sarkozy's camp said she was a gaffe-prone lightweight, a tax-and-spend Socialist unable to keep her cool.
The pair have offered contrasting visions of France, Royal combining left-wing economic policies and consensual approach to social affairs in a ''change without brutality'' reform package.
Sarkozy campaigned for the ''silent majority'' of hard-working French people, vowing real change with reforms that would shake up a hide-bound economy to foster growth, jobs, spending power and restore national identity.
He topped the first round vote on 22nd April with 31.2 per cent of the ballot against 25.9 per cent for Royal. Turnout was almost a record at 84.5 per cent. - DDNews India
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