The 89-year-old president, Africa's oldest leader, is running for election for the seventh and perhaps final time, after a series of violent crackdowns, economic crises and suspect elections.
But on the eve of the vote, Mugabe vowed to step down if he lost and claimed the army -- long the bulwark of his rule -- would also respect a victory for Morgan Tsvangirai, his perennial rival.
"If you lose you must surrender," the firebrand said at a rare press conference in Harare just hours before the polls open at 0500 GMT.
While this year's campaign has seen little of the bloodshed that marred the 2008 election, the 61-year-old former trade union leader has raised alarm about silent manipulation.
Tsvangirai's Movement for Democratic Change yesterday handed what it claimed was documentary evidence of plans to rig the election to observers from the Southern African Development Community (SADC).
The dossier, which was seen but could not be independently verified by AFP, listed examples of duplicate or questionable voters gleaned from a initial examination of the electoral roll.
"We have seen a lot of duplicate names in the roll, where you see somebody is registered twice, same date of birth, same physical address but with a slight difference in their ID number," junior minister Jameson Timba told AFP.
An SADC observer who asked not to be named said the MDC dossier raised serious questions.
"It's not normal. If the roll had been released two weeks ago, these kind of problems would have been fixed."
"We do remain concerned about the lack of transparency in electoral preparations by continued partisan behaviour, by state security institutions, and by the technical and logistical issues hampering the administration of a credible and transparent election," she said.
Mugabe vehemently denied ever rigging the vote. "We have done no cheating, never ever."
Final results are expected with five days. The elections will also chose lawmakers and local government councillors.
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