The former soldier, who staged a remarkable recovery from cancer this year, and wants a new six-year term to consolidated his Bolivarian revolution, is in a fight.
His opponent is 40-year-old Henrique Capriles Radonski, an energetic state governor who offers the opposition, for the first time in Mr Chávez's long tenure, hope of overcoming the man who for two decades has been South America's rabble-rouser-in-chief.
Although polls in Venezuela are notoriously unreliable, one of the more respected firms, Datanálisis, puts Mr Chávez 10 points ahead, while another, has them neck and neck.
The 58-year-old has led Venezuela for 13 years, under a banner of 21st Century socialism, with help from his mentor Fidel Castro across the water in Cuba.
The president is able to inspire a quasi-religious fervour among his supporters who know him as El Comandante. Last night in Caracas they were due to sing with him, walk alongside his motorcade for miles and scream his every word.
"I believe in the Revolution; I believe in Chávez," shouted teacher Haydee Nabarro, 51, at a recent rally, echoing many of the thousands that turned up.
Mr Capriles' rallies have also been impressive, bringing in a large part of Venezuela's electorate that has had enough. They have not always gone smoothly though. On Saturday, three opposition activists were killed by gunmen reportedly firing from a government-branded vehicle.
Venezuelans are used to it, however, as they face one of the world's highest murder rates. With figures in Caracas comparable to war zones such as Baghdad, insecurity is the major election theme and many are worried that the president will not go quietly should he lose on Sunday. Much of his support comes from the poor in the barrios, many of whom are armed.
Despite his wealthy background, Mr Capriles has gained much support in the slums. He has worked tirelessly, much like Mr Chávez did before his own election in 1998, travelling around the country meeting with as many people as possible.
Mr Chávez's use of state resources, such as compulsory airtime across television networks, has tipped the balance in the government's favour in what critics describe as an unfair fight. The president rarely calls Mr Capriles by name, often referring to him as the "candidate of the Right" or simply "the loser".
Mr Capriles has suffered attacks by state media. The government television network read out accusations about his sex life and a government website attacked his Jewish roots in an essay titled "The Enemy is Zionism".
With the world's biggest oil reserves, Mr Chávez's government can afford to be combative. The country has floated on high oil prices the past few years, the money funding social projects that critics decry as government vote buying. Those who have been pulled from poverty and given free housing see things differently.
"My life has changed," said Miguel Calanon, 42, who lives in a house given to him by the government just outside Caracas. "No other government has ever helped me."
There are many more waiting, however. "Everyone has a friend of a friend who's been helped by the government," said Yesman Utrera, 24, speaking in his own barrio in the west of Caracas.
Those who receive government aid, shopping at subsidised socialist supermarkets, for example, are insulated from near 25 per cent annual inflation, the highest in the Americas.
As well as rampant crime, an out-of-control economy and regular electricity blackouts, Venezuelans must also consider whether Mr Chávez will survive another six years.
Mr Chávez announced that he was suffering from cancer last June and has spent a number of months since then shuttling between Caracas and Havana for treatment.
While the topic has fallen off the radar in recent months, thanks in part to the immense public relation skills of the Chávez regime, it is still on the minds of investors who have pushed bonds to rally in recent months, hoping for a change of government either in elections or a downturn in Mr Chávez's health.
"The candidate of the government reached office with good intention, but he's no longer interested in change, he's sick with power," Mr Capriles said this week. "This government's time is up."
By Girish Gupta, The Telegraph, October 4, 2012