The presidential vote pits five candidates against one another, with incumbent Bakili Muluzi of the ruling United Democratic Front (UDF) forbidden to run again because he has already served two five year terms.
The main contenders in the presidential race are 72-year-old economist Bingu wa Mutharika of the UDF and Gwanda Chakuamba, 69, who formerly served as a top aide to the country's long-time dictator, Kamuzu Banda.
Mutharika is seen as the odds-on favourite to win the presidency, mainly because the opposition has been unable to unite behind a single candidate.
Chakuamba, his main opponent, heads the Mgwirizano (Unity) Coalition of seven new parties, but a further three candidates are likely to split the opposition vote.
They include John Tembo, 72, another former lieutenant of Banda, who will stand on the ticket of the Malawi Congress Party (MCP), the oldest political grouping which led Malawi to independence from Britain in 1964.
Brown Mpinganjira, 55, former senior minister and top aide to Muluzi, is also gunning for the presidency under the flagship National Democratic Alliance (NDA), as is 60-year-old Justin Malewezi, former vice president in the Muluzi administration, the first independent presidential candidate.
Mutharika is expected to cast his vote at Goliati School, near his home village of Kamoto in Thyolo district, 50 kilometres east of Blantyre, the commercial capital.
Malawi, a former British colony wedged between Mozambique and Zambia, is one of the poorest countries in the world, with a per capita income of $210 and most people living on less than a dollar a day.
It is also one of the hardest-hit by acquired immune deficiency syndrome, or Aids.
Muluzi has led the country since he defeated Banda in the country's first multi-party polls in 1994.
In 2002 lawmakers rejected a proposal to amend the constitution to let him run for a third term.
A total of 1 254 candidates - 356 of them independents - are fighting for parliamentary seats.
Some 5,7-million Malawians are eligible to cast their ballots, and the voting is being monitored by over 200 international observers from the European Union, the Commonwealth and the African Union.
Polling at 3 884 centres throughout the country opened at 6:00 am and was due to end at 6:00 pm. - Sapa-AFP
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