A candidate needs 50 percent of the vote to avoid a run-off and both Mugabe and Tsvangirai appear confident they can manage that feat.
Mugabe has focused his campaign on bashing homosexuals and on promises to widen the redistribution of wealth to poor black Zimbabweans.
Amid recovery from an economic crisis that saw mass unemployment and galloping inflation, Mugabe loyalists insist their hero is “tried and tested”.
Credible opinion polls are rare, but according to one survey by the US-based Williams firm in March-April, Mugabe could be in for a rough ride.
In a survey of 800 Zimbabweans, 61 percent said they had a favourable view of the MDC compared with 27 percent for Mugabe’s ZANU-PF.
The poll showed Tsvangirai leading in seven of 10 provinces and that only 34 percent of those who voted for Mugabe in 2008 back him for president this time around.
Tsvangirai hopes his plans to lure back foreign investors, create a million jobs in five years and improve public services will deliver a long-awaited victory.
Polling stations will close at 7pm (1700 GMT). Final results are expected with five days.
The elections will also chose lawmakers and local government councillors.
In June, the Research and Advocacy Unit – an NGO – reported the existing roll included one million dead voters or people who have emigrated, as well as over 100,000 people aged over 100 years old.
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