Polling began at 0600 GMT in the tiny West African nation -- long considered a democratic success story in the troubled region. Voting was due to end nine hours later.
Mathieu Boni, an official from a civil society group which has deployed more than 3,000 election observers, said "more than half" of the nearly 8,000 polling stations across the country opened on time.
Incumbent President Thomas Boni Yayi is bowing out after serving a maximum two five-year terms. The first results are expected within 72 hours of the vote.
The 61-year-old is standing for the ruling Cowry Forces for an Emerging Benin (FCBE) party and is widely viewed as Boni Yayi's chosen successor.
He already has the support of two opposition parties and on Friday dismissed critics who see him as an outsider "parachuted" in by former colonial power France.
"People say I'm white, an interloper, a foreigner, a Frenchman, a colonialist," Zinsou told AFP. "But there's perhaps 10 per cent of people who act like that.
Zinsou, who in the 1980s was a speechwriter for France's socialist former prime minister Laurent Fabius, said he had also encountered people who were proud of his success abroad.
Two of Benin's leading businessmen, Patrice Talon, 57, nicknamed "The King of Cotton", and "The Chicken King" Sebastien Ajavon, are also seen as front-runners, pitching for the top job after previously bankrolling presidential bids from the sidelines.
Other favourites include economist Abdoulaye Bio Tchane and financier Pascal Irenee Koupaki, both 64.
But with so many candidates, political analysts predict no decisive result and believe whoever wins in the northern region will determine the overall result.
In Benin's business capital Cotonou, farmer Emile Sosa was one of the first to vote in the city's Cocotiers district.
"I want the next president to encourage the youth to take to agriculture," the 49-year-old father of four said, lamenting that the young were increasingly taking to driving motorcycle taxis due to a lack of opportunities.
The first round of voting had been due to take place on February 28 but was rescheduled because of delays in the production and distribution of the 4.7 million voters' cards.
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