The three candidates are incumbent President Bashar al-Assad, former minister Hassan al-Nouri and lawmaker Maher Hajjar, Xinhua reported.
Syria's interior ministry said that more than 15 million registered voters will cast their ballots at 9,610 polling stations across Syria.
The poling offices will remain open from 7.00 a.m to 7.00 p.m.
The government has reportedly set up ballot boxes in shelters to allow thousands of displaced Syrians to participate in the election.
The vote is taking place despite its rejection of the opposition and their Western backers, who have dismissed the election as a "farce."
Syrians living overseas cast their ballots last week.
Syrian nationals, mainly in Malaysia, China, South Korea, India, Indonesia, Lebanon, Venezuela, Jordan, Iran and Oman, voted at the Syrian embassies and consulates in these countries.
The election will be the first in half a century. Previously, there were only referendums to support Assad or his late father Hafez al-Assad, who was in office from 1971 to 2000.
In 2007, Bashar al-Assad won seven more years in office with 97 percent of the vote in a nationwide referendum on his leadership, in which he was the only candidate.