The ministers, meeting in Innsbruck, Austria, will also review plans for EU nations to pool a small part of their defence budgets for co-operative research - a move critics denounced as a threat to national control over military affairs.
The possibility of more EU assistance to the faltering international peacekeeping mission in Sudan will also feature during the two-day meeting.
A request from the UN for EU troops to bolster the 16,000-strong mission in Congo has underscored the EU's difficulties in building up its own effective military capability.
Although the plan only entails a few hundred highly mobile troops able to rush to potential trouble spots for a few months as Congo holds its elections, the EU has struggled to find nations willing to lead or contribute to the force.
Tony Blair has long sponsored the idea of a rapid reaction force, made up of EU member nations and able to be flown to trouble spots across the globe. The Prime Minister's attempts to gain acceptance of such a force have mired over questions of political control.
As far as Congo is concerned, at a meeting of EU foreign ministers last week in Brussels, diplomats said France, Germany, Sweden and Belgium had stepped forward, although some were insisting on strict conditions as to how their troops could be used.
Officials hope for firmer offers to come from the Innsbruck meeting, although they said much depends on a debate expected later in the month in Berlin on the possible deployment of German troops.
EU officials in Brussels said options under discussion included the deployment of 200 to 450 European soldiers to the Congolese capital, Kinshasa, ahead of the 18 June presidential election.
Up to 800 additional troops would be held on standby outside Congo, ready for rapid intervention if there is trouble.
On Sudan, George Bush, the US president, has lobbied European leaders for a greater international involvement to help an African peacekeeping force which has proved unable to contain ethnic violence in the Darfur region.
A proposal to create a fund of 134 million for joint research on defence technology would mark a small but potentially significant step toward increased EU defence co-operation. Critics claim it could lead to nations handing control over military spending to the EU and warn that could undermine transatlantic ties.