Prime Minister Lionel Zinsou, a former investment banker, faces Patrice Talon, the "king of cotton" in a presidential run-off.
President Thomas Boni Yayi is standing down after serving two terms in office.
A tight race is expected after Mr Zinsou gained 28% in the first round, just ahead of Mr Talon's 25%.
As he cast his vote, Mr Zinsou said the campaign had been "dignified, calm and peaceful. A model for Africa".
He said he hoped the country would stay peaceful on the day of the vote and the coming days.
Mr Talon used to be a close ally of President Boni Yayi but was accused of masterminding a plot to poison him in 2012.
He fled to France but returned last year after receiving a presidential pardon.
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