The vote comes at a time when citizens of the Latin American state are struggling to cope with widespread food shortages, the collapse of their traditional currency and relentless hyperinflation — which the International Monetary Fund (IMF) has forecast to hit 13,000 percent in 2018.
At the same time, almost 75 percent of Venezuelans are reportedly suffering from weight loss while unemployment in the country is expected to skyrocket to 32 percent over the next four years.
Yet, with the country's mainstream opposition boycotting the vote — and two of its most popular leaders barred from running — the socialist incumbent is seen on the brink of securing a fresh mandate to serve as premier for another six years.
"Maduro will win… the opposition is completely demoralized and broken. In fact, they are even unsure if the boycott is the right way to go because divisions between the two candidates only helps Maduro's cause," Nicholas Watson, Latin America analyst at New-York based Teneo Intelligence, told CNBC in a phone interview.
An abstention push from Maduro's political opponents, on the grounds that voting conditions in the oil-dependent country are unfair, has left the outcome of the ballot in little doubt.
Nonetheless, Watson said the boycotting strategy was not completely without merit.
"It actually could be quite an effective tactic if national and international photographers have nothing but sparse queues to take pictures of. Okay, the government will probably respond with pictures of slightly busier voting booths, but that could still spark a propaganda war."
Maduro's main political rival is former state governor Henri Falcon, who broke with the opposition coalition in order to stand for election, insisting the only way to remove the incumbent would be to defeat him at the ballot box.
While polling in the country is somewhat unreliable given the larger-than-expected abstention rates, some projections do show Falcon ahead of Maduro.
Regardless, even if Falcon or another political opponent could win the vote, analysts say he would most likely be hamstrung by Maduro's allies. The current president controls the military and effectively every branch of government.
Meanwhile, President Donald Trump is thought to be considering adding targeted crude sanctions to measures already taken to stop Venezuela issuing more debt. External observers have said such a move would constitute the "death knell" for the OPEC member's economy.
"Oil sanctions would be devastating to the Venezuelan economy and to the regime's internal stability as they would very strongly impact the revenues that flow through the patronage regime," Fernando Freijedo, Latin America analyst at the Economist Intelligence Unit, told CNBC via email.
Maduro's leftist administration is almost entirely dependent on crude sales in order to try to decelerate its spiraling crises.
Venezuela's production collapse has seen its crude output drop to around 1.4 million barrels a day (bpd) in recent months — a spectacular fall of nearly 40 percent since 2015.
"Whether sanctions are enacted or not, it is very likely that reasonably soon — say, within the next 12 months — there will be an internal crisis in the regime as the patronage system that ensures internal stability becomes eroded. That will be a key moment for Venezuela," Freijedo said.