He was the mayor of Zvečan, a predominantly Serb community in the disputed territory of Kosovo, from 2002 to 2013, serving as a member of the Democratic Party of Serbia (DSS).
The Serb List began a boycott of the Republic of Kosovo's political institutions in November 2022, and Milović submitted his resignation in Zvečan's assembly at that time.
He was quoted as saying, "We Serbs from Kosovo-Metohija cannot be represented by the so-called Provisional Executive Council [set up by the Belgrade authorities] at the forthcoming [...] negotiations with the Albanians.
[14] At a protest in early 2006, Milović said that "a settlement to the status of Kosovo must be arrived at through compromise, international law and the borders must be respected, there must be no winners and losers.
"[15] Later in the year, he welcomed the approval of a new Serbian constitution that recognized Kosovo and Metohija as an integral part of the country with significant autonomy.
[16] The Serb community in northern Kosovo generally boycotted the 2007 Kosovan local elections, which took place against the backdrop of the province's drive for independence.
Although not recognized internationally, the vote provided de facto legitimacy to the governing authorities in Zvečan and in the neighbouring municipalities of Leposavić, Zubin Potok, and northern Kosovska Mitrovica.
"[19] Milović condemned an attack on an Albanian-owned bakery in Zvečan in 2010, saying, "the Albanians, citizens of our municipality, ten years since the arrival of the UN mission, have had no problems.
Milović was a leader of the community's actions, working alongside fellow mayors Slaviša Ristić of Zubin Potok, Branko Ninić of Leposavić, and Krstimir Pantić of northern Kosovska Mitrovica.
The Belgrade and Priština governments announced a deal in August 2011 that would have seen Kosovo Force continue to guard the Jarinje and Brnjak crossings.
Addressing a crowd of protesters, Milović said, "We will stay at the barricades because as mayors of northern Kosovo we are obliged to respect the opinion of the local people.
[22] A December 2011 report in the Serbian paper Blic described Milović as the second-most important figure, after Slaviša Ristić, in coordinating the Serb community's actions; both mayors were described as enjoying support from their electorate that transcended normal party divisions.
[28] The agreement normalized some aspects of the relationship between Belgrade and Priština without addressing the status of Kosovo; the Serbian government attempted to win local support for the deal, though ultimately both Ristić and Milović opposed it.
[29] The Serbian government dissolved the assemblies of Zvečan and other the three Serb municipalities in northern Kosovo in September 2013, thereby ending Milović's tenure as mayor.
Milović ultimately ended his boycott and was a mayoral candidate in the 2017 local elections, running for his own "For Our Zvečan" party in an alliance with Oliver Ivanović.
[35][36] Following Ivanović's assassination by unknown parties in early 2018, Milović gave an interview in which he lamented the power of organized crime in northern Kosovo.