Polling stations opened at 8:00 am for the West African nation's 2.1 million voters, and are expected to close at 6:00 pm.
They will choose a successor to President Ellen Johnson Sirleaf, who is stepping down after serving 12 years as Africa's first elected female leader.
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Reports from early voters suggested that problems with queue control and voting ID encountered in the October 10 first round and the subject of a bitter legal battle waged by Boakai had been addressed for the run-off.
"This time everything is OK. It was very easy for me to find my voting place. Already at the entrance someone is there to direct you," said Gabriel Peters as he cast his vote at Calvary Chapel Mission School in Monrovia, which he said had opened on time.
Malcolm Joseph, a local observer and the executive director of the Center for Media Studies and Peace Building, told AFP the country had "resolved to move ahead" with what he expected to be "a very peaceful process".
In the first round of voting on October 10, Weah topped the poll with 38.4 percent while Boakai came second with 28.8 percent, triggering a run-off as neither made it past the 50 percent needed to win outright.
Boakai then accused the NEC of fraud and incompetence grave enough to have affected the vote, delaying proceedings while the complaints were analysed by the Supreme Court. His party's arguments were ultimately rejected.
Whoever wins the delayed vote faces an economy battered by lower commodity prices for its main exports of rubber and iron ore, and a rapidly depreciating currency.
Both candidates have been accused of offering vague platforms, beyond assurances on free education and investment in infrastructure and agriculture.
As Liberia's most famous son, Weah attracts huge crowds and has a faithful youth following in a country where a fifth of the electorate is aged 18 to 22, but he is criticised for his long absences from the Senate, where he has served since 2014.
Weah's endorsement by warlord-turned-preacher Prince Johnson, who is extremely popular in the populous county of Nimba, may boost his chances, while he was pictured at a public event with Sirleaf on Thursday, heightening speculation a feud with Boakai has pushed her to support his opponent.
(Only the headline and picture of this report may have been reworked by the Business Standard staff; the rest of the content is auto-generated from a syndicated feed.)
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