"I can not vote for those who have tormented me", Mugabe said, in a reference to Mnangagwa, who took office with the military's support.
"I hope the choice of voting tomorrow will throw, thrust away the military government and bring us back to constitutionality", said a frail looking Mugabe, in a rambling off the cuff speech that lasted nearly an hour.
Utoile Silaigwana‚ the ZEC acting chief elections officer‚ condemned Chamisa for violating the law by holding a press briefing and said he had since been reported to the police. He acknowledged that there was a "good turnout". Excitement at the prospect of change spurred voters to form long queues outside polling stations across the country long before doors opened at 7am. Anyone in line as of the 7 p.m. closing time could still vote, though opposition parties were concerned that their supporters could drift away if forced to wait for hours.
There have been reports of intimidation and coercion in the build-up to the vote and state media is biased towards the ZANU-PF, but there is a consensus that the process has been better than before.
About 5.5 million people were registered to vote in this southern African nation anxious for change after economic and political paralysis during the almost four-decade rule of 94-year-old Mugabe.
There will be a runoff on September 8 if no candidate wins more than half the votes.
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"I have nothing to do with what president Mugabe would want to say as a voter". I am not leaving anything to chance. First violation will result in booking of case and attract Rs 25,000 penalty, whereas the second time Rs 50,000 fine would be slapped.
Chamisa voted in Kuwadzana, a poor suburb in Harare where he has been an MP for the past 18 years. He said he hoped voting in rural areas would be fair.
He had earlier told a cheering crowd as he cast his vote: "Victory is certain, the people have spoken", reported Reuters news agency. He had his finger inked and was assisted by his wife into the booth.
According to the Zimbabwe Electoral Commission (ZEC), close to 5.5 million Zimbabweans registered for the polls, 20,000 of whom are new voters.
"After years of stasis the events of November 2017 gave Zimbabwe the chance to dream again", Mnangagwa said on Sunday in an address on state radio.
Parliamentary and local elections are also taking place on Monday. Polling officers helped voters put each ballot paper in the right box. "The place has changed", said Patrick Musemburi, a 37-year-old minibus taxi driver in the capital Harare.