His likely main rival among the eight contenders for the ceremonial post is Dragan Primorac, backed by the Croatian Democratic Community (HDZ), which currently rules the country.
The election comes at a time when the EU and NATO member state with a population of 3.8 million is struggling with severe inflation, widespread corruption and labour shortages.
According to an opinion poll conducted on December 27, Milanovic is supported by 37 percent of voters, while Primorac has the backing of 20 percent.
But with neither candidate expected to garner more than 50 percent of the vote to win outright, the new head of state is likely to be elected in a second round in two weeks.
During the campaign, the two main rivals often exchanged insults, with Milanovic deriding Primorac as boring and "as fake as a 13 euro note".
Croatia's president commands the country's armed forces and has a say in foreign policy.
Despite its limited powers, however, many believe the post is key to the political balance of power.
Since independence in 1991, Croatia has been governed mainly by the HDZ.
Milanovic, a former leftist prime minister, has been one of the leading and most colourful political figures in Croatia for almost two decades.
Milanovic, 58, won the presidency for the opposition Social Democratic Party (SPD) in 2020 on promises to stand for tolerance and liberalism.
However, he has used his post to attack his political opponents and EU officials, often with insulting and populist rhetoric.
Milanovic, who has condemned Russia's aggression against Ukraine, has nevertheless criticised Western military aid to Kiev.
This led Prime Minister Andrej Plenkovic to describe him as a pro-Russian who is "destroying Croatia's credibility in NATO and the EU".
Milanovic countered that he wanted to prevent Croatia from "getting involved in a war".
"As long as I am president, no Croatian soldier will fight foreign wars," he said this month.
He regularly scolds Plenkovic and his HDZ party for systemic corruption, calling the prime minister "a serious threat to Croatian democracy".
"I am the guarantor of curbing the octopus of corruption...led by Andrej Plenkovic," he said during the campaign.
For many, the election is a continuation of a long-running feud between two powerful politicians.
"It's still about the conflict between the prime minister and the president. Everything else is just side issues," said political analyst Zarko Puhowski.
Primorac, 59, campaigned as a "uniter" who promoted family values and patriotism.
The elections will show "whether Croatia is heading towards the East or the West...towards division or unity", he said.
A doctor and scientist returning to politics after 15 years, Primorac has repeatedly accused Milanovic of "bringing Croatia into disrepute".
Critics, however, argue that Primorac lacks political charisma and credibility and has only served as an attack dog for the HDP to provoke Milanovic.
Polling stations open at 7:00 a.m. (local time) and close twelve hours later, when exit polls are expected.
Official results are expected late on the 29th of December. | BGNES