Lines of voters snaked around a school in Harare, where polling booths opened just after the scheduled time of 7 am (0500GMT) today.
Many were dressed in heavy coats to ward off the winter chill. Some had flasks of hot drinks.
Voter Isaac Rufaro says he joined the line before dawn, noting: "We have got to get this done."
The contest pits Mugabe against Prime Minister Morgan Tsvangirai, the former opposition leader who teamed up with the president's party in an uneasy coalition.
