The main rivals are current Vice-President Salvador Sanchez Ceren of the left-wing FMLN party and Norman Quijano of the conservative Arena alliance.
Neither is expected to win outright because a third candidate standing for a new independent party is likely to make a strong showing.
The campaign has been dominated by poverty and crime. El Salvador’s murder rate is among the highest in the world.
Correspondents say there are signs that a recent truce agreed between the two main street gangs is falling apart.
Salvador Sanchez Ceren, 69, was a rebel commander when the Farabundo Marti National Liberation Front (FMLN) was a guerrilla group during the 1980-1992 civil war.
He has promised to tackle crime through education and social programs.
Opinion polls suggest he had a lead over Norman Quijano, who stood down from his position of mayor of San Salvador to stand for president.
Many voters are critical of the 2012 truce with gangs, and Norman Quijano has accused the administration of outgoing President Mauricio Funes of negotiating with criminals. He is advocating tougher policies against drug gangs.
The truce has led to a decrease in El Salvador’s murder rate, but gradually the number of killings is going back up.
Analysts say the vote may hinge on the popularity of the third candidate, former President Antonio Saca who is running for the new Unidad party.
The second round of voting, if needed, is to be held on March 9.
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