A calm day of ballot casting with long lines across the nation gave way to counting after polls closed, capping a campaign hailed for vibrant and violence-free debates and rallies in the small West African nation.
Frontrunners include footballing icon George Weah, incumbent Vice President Joseph Boakai, longtime opposition figure Charles Brumskine and former Coca-Cola executive Alexander Cummings.
Also waiting in the wings with potentially significant vote shares are telecoms tycoon Benoni Urey and former central bank governor Mills Jones.
"If you are in a queue by 1800 hours you will be allowed to vote," he said for those still waiting in long lines.
Some voters who appeared at the wrong polling place or were registered more than once were unable to cast their ballot, he admitted, without putting a figure on those affected.
The first official results could be released as early as today afternoon, an NEC official told AFP.
"It's been very peaceful and organised," Joe Pemagbi, an electoral observer for the Open Society Initiative for West Africa, a civil society group, told AFP.
The vote is a crucial test of Liberia's stability. Sirleaf, Africa's first female elected head of state, is stepping down after a maximum two six-year terms in which she steered the country away from the trauma of civil war, but, say critics, failed to tackle its poverty.
The nation's 2.18 million registered voters made their choice from a crowded field of 20 presidential candidates -- although just one of them is a woman -- and elected 73 seats in the lower chamber, the House of Representatives.
Back-to-back civil wars, the 2014-16 Ebola crisis and slumped commodity prices have left Liberia among the world's poorest nations, while corruption remains entrenched.
In Monrovia, poor and young voters seem to overwhelmingly favour Weah, although his choice for vice-president in Jewel Howard-Taylor, the ex-wife of Liberian warlord Charles Taylor, may hit his support in other areas of the country.
"I think he will bring development," sad Grace Dennis, a 24-year-old student, as she cast her vote at the University of Liberia. "People are graduating with no jobs."
If no candidate wins 50 percent of the presidential vote, then a run-off of the top two contenders will be held on November 7 -- an outcome analysts say is a near certainty.
Boakai, Weah's most significant rival, has undertaken a delicate balancing act to promote his record in government while distancing himself from Sirleaf to define his own vision.
"To rebuild after war is very costly. This government has done some tremendous things," Gbazeki commented, waiting near the end of an hours-long queue.
Upstart businessman Cummings has eaten into Weah's support among Liberia's youth, and his fans were also out in force across polling stations.
"We need a new breed of leaders. Mr Cummings is educated and that is what Liberians need most. Education brings insight," pastor Fred Slocum told AFP, joining a line at William VS Tubman high school.
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