Five candidates are competing for victory in the election: incumbent President Nicolas Maduro, editor at the Aporrea media outlet Reinaldo Quijada, conservative preacher Luis Ratti, opposition leader Henri Falcon and Evangelical pastor Javier Bertucci.
The polling stations will open at 06:00 a.m. local time (10:00 GMT) and close at 06:00 p.m.
The presidential elections were initially set to take place in December, then rescheduled for April 22, and delayed again to May.
Venezuela has been facing mass protests since last spring. The protests were sparked by the country's top court's decision to restrict the legislative powers of the parliament as well as the election to the National Constituent Assembly initiated by Maduro with the intention of changing the constitution.