The Netherlands and Belgium oppose any moves to integrate Serbia, saying the country has shown insufficient co-operation with the UN war crimes tribunal at The Hague.
The tribunal is still searching for Ratko Mladic and Radovan Karadzic, who led the Serb faction during Bosnia's civil war in the early 1990s.
A proposed Stabilisation and Association Agreement would offer trade and co-operation advantages to Serbia, as well put it on track for open membership talks with the EU.
Supporters of the deal believe that signing the agreement before Serbia holds its second round of presidential elections on February 3 would give a boost to Boris Tadic, the pro-Western incumbent.
Support for Tomislav Nikoli, Tadic's nationalist opponent, has grown amid dissatisfaction with international support for Kosovo's independence drive.
"We should ... help Serbia on its approach to the European Union," said Dimitrij Rupel, the Slovenian foreign minister.
"One of the forms of such assistance, or a sign of closeness, should be a signature of [the] Stabilisation and Association Agreement in the coming days."
However, diplomats said firm Dutch opposition makes it unlikely that the
agreement could be signed when Serbia's foreign minister, Vuk Jeremic, joins his EU counterparts.
Rupel will chair Monday's meeting, the first to be held by EU foreign ministers since Slovenia took over the EU's rotating presidency on January 1.
Kosovo's independence will loom large at the meeting.
Hashim Thaci, Kosovo’s prime minister said last week that his country's declaration of independence could be days away.
The issue has opened a deep rift between Western nations and Russia, which backs Serbia's opposition to Kosovo's independence.
Ban Ki-moon, the UN secretary-general, said on Friday that he could not yet approve a planned 1,800-strong EU policing mission in Kosovo because of international dispute over province's future.