They will have a choice of 27 candidates as they vote for the first time since last year's military coup upended one of the region's most stable democracies, as Islamist militants hijacked a separatist uprising to seize much of the country.
The ballot is due to open under heavy security after one of the main Islamist armed groups in northern Mali said Saturday it would "strike" polling stations.
"The polling stations and other voting places for what they are calling the elections will be targeted by mujahideen strikes," the Movement for Oneness and Jihad in West Africa (MUJAO) said in a statement carried by the Mauritanian ANI news agency.
It did not specify what form the attacks would take.
The group warned Malian Muslims against taking part in the election, ordering them to "stay away from the polls".
Although the three-week campaign ended on Friday without major incident, it played out in the shadow of violence in the north that has cast doubt over Mali's readiness to deliver a safe and credible election.
Critics at home and abroad have argued that Mali, under pressure from the international community, is rushing to the polls and risking a botched election that could do more harm than good.
But Louis Michel, the head of the European Union observation mission, sounded a note of optimism on Friday, saying conditions had been met for a credible first round.
"I believe that these elections can take place in a context and in conditions that are acceptable and do not allow for a distortion or an abuse of the result," he told reporters in the capital Bamako.
Much of the worry ahead of the polls has been focused on Kidal, occupied for five months by Tuareg separatists until a ceasefire accord allowed the Malian army earlier this month to provide security.
Clashes between Tuaregs and black Africans in the run-up to the election left four people dead. And gunmen thought to be from the National Movement for the Liberation of Azawad (MNLA) have kidnapped five polling officials 200km north of Kidal.
The ballot will be the first since the military mutiny in March last year that toppled democratically elected president Amadou Toumani Toure. The ensuing confusion helped the MNLA, MUJAO and other groups allied to al-Qaeda to seize northern Mali.
On the eve of the election, acting president Dioncounda Traore, in a televised address, urged Malians to ensure a massive turnout in a country where the participation rate is usually around 40%. Traore himself is not a candidate.
A UN peacekeeping mission integrating more than 6 000 African soldiers into its ranks is charged with ensuring security on Sunday and in the months after the election. By the end of the year it will have grown to 11 200 troops and 1 400 police.
The deployment allows France to start withdrawing most of the 4 500 troops it sent to Mali in January to stop the Islamists from advancing towards Bamako from their northern strongholds.
Haidara Aichata Cisse, the only woman in the race, will go head-to-head with 26 men, including past premiers Ibrahim Boubacar Keita, Cheick Modibo Diarra, Modibo Sidibe and Soumana Sacko.
Keita is seen as the main frontrunner alongside Soumaila Cisse, a former chairperson of the Commission of the West African Monetary Union. – AFP