"I cast my vote, I feel happy and proud as a citizen of Afghanistan," he said after voting in a school near the presidential palace in Kabul.
"Today is an important day for our future, the future of our country. I urge the Afghan nation to go to the polling station despite the rain, cold weather and enemy threats... and to take the country another step towards success."
Karzai has vowed to stay neutral in the election and oversee a free and fair vote, despite allegations of massive fraud in the 2009 poll when he retained power after a long and disputed process.
The president, who has ruled since the fall of the Taliban in 2001, says he will live as a private citizen in Afghanistan after leaving the palace, but he is expected to retain extensive political influence.
In the first hour of voting there were no major attacks from Taliban insurgents who have vowed to target the election.
Security forces across the country were on alert to protect voters, election staff and polling stations.
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