Stojiljkovic shot himself on the steps of parliament
Vlajko Stojiljkovic, who headed the police under former President Slobodan Milosevic, pulled out a gun and shot himself in front of the federal parliament building in Belgrade.
In a suicide note, Mr Stojiljkovic said he was acting in protest at parliament's adoption of a law allowing the transfer of war crimes suspects to The Hague, just hours earlier.
Yugoslav President Vojislav Kostunica described the suicide attempt as a "warning to the international community that constantly sets conditions, pressures us and dictates behaviour".
'No surrender'
Mr Stojiljkovic, who is still a member of the federal parliament for Mr Milosevic's SPS party, is one of four senior officials accused alongside Mr Milosevic for alleged war crimes during the Yugoslav military campaign in Kosovo.
He pledged never to surrender to the tribunal.
During his time as interior minister, from 1998 to 1999, police units are alleged to have committed atrocities against ethnic Albanians in Kosovo.
The tribunal has already begun hearing the case against Mr Milosevic, who faces 66 charges, some of which cover the Kosovo campaign.
Government blamed
"By this act I, as a deputy of the federal parliament, express my protest against all members of the puppet authorities," said the note, which was read out by Radical Party member of parliament, Aleksandar Vucic in front of the parliament.
"I accuse them of destroying Yugoslavia with the assistance of our greatest foreign enemy... for ruthless violation of the constitution and laws of this country, the policy of treason and capitulation, ruin and suffocating of our national dignity," the note read.
"Patriotic citizens of this country will know how to avenge me," Mr Stojiljkovic wrote.
'Quick handovers'
The law passed by parliament on Thursday allows for the handing over of about 20 suspects, including Mr Stojiljkovic.
It was approved in the lower house with 80 votes for and 39 against. The upper house approved it on Wednesday.
Before the law was passed, Yugoslav Interior Minister Zoran Zivkovic said that the first extraditions could take place very soon, with all the suspects being transferred to The Hague by 1 May.
The Yugoslav Government has been under pressure from the United States to start extraditing suspects.
The US effectively froze $40m of aid after Yugoslav authorities failed to meet a 31 March deadline to act.