Just 18 months after President Edgar Lungu narrowly won office in a snap election, he and his main rival Hakainde Hichilema face off again in a field of nine candidates.
Only 27,757 votes separated the two candidates in the 2015 ballot.
At least three people have been killed during the campaign, with regular clashes erupting between supporters of Lungu's Patriotic Front (PF) and Hichilema's United Party for National Development (UPND).
Ahead of the vote, the election commission issued an emergency statement describing the unrest as "unprecedented" and warning it had "marred Zambia's historic record of peaceful elections".
But skirmishes continued until polling day, including fighting in the streets and vehicles overturned close to Hichilema's final rally on Wednesday in Lusaka.
UPND supporter Patricia Situmbeko, 50, blamed the violence on Lungu, who she said had failed to reign-in his supporters.
"Zambia was peaceful but the president got his cadres excited and they attack the UPND people," the mother-of-five told AFP at a voting station in the low-income Mtendere district of Lusaka.
"We voted UPND for real change... The youth are unemployed, there is too much violence and the cost of living is rising so fast. Sugar is nearly up by three times in price over recent years."
"There have been a lot of promises and people are expecting a lot from this election, but I think that people might want to stay with the same president for now... I don't sense the people all demanding a new president yet," he said.
Constitutional changes mean that the winner must now secure more than 50 per cent of the vote, meaning a second round run-off could be held within weeks, raising the spectre of further hostilities.
"The PF government of President Lungu is starting to panic as the UPND campaign gains sustained momentum," said Robert Besseling, of EXX Africa consultancy.
Zambia, in contrast to some of its neighbours such as Angola and Zimbabwe, has escaped war and serious upheaval since independence from Britain in 1964.
It last held a peaceful transfer of power to an opposition party in 2011 when Michael Sata took office.
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