Diplomats said that Greece as current EU president had called the six-nation meeting to try and coordinate policy on Iraq among European members of the United Nations Security Council.
France and Britain are permanent veto-exercising members of the UN Security Council while Spain and Germany have just joined the body for a two-year term.
Also attending the meeting is Italy which will take over the EU presidency from Greece on July 1.
Participants of the unusual encounter also include EU security chief Javier Solana as well as European External Relations Commissioner Chris Patten.
The EU meeting comes only hours before the sharply divided Security Council hears a key report from the chief weapons inspectors on Iraq's alleged nuclear, chemical and biological arms programme.
The report by Hans Blix marks 60 days of UN inspection activities in Iraq.
Blix has already said the inspectors have found no "smoking guns". He has also pointed to a "mixed bag" of cooperation from the Iraqis.
EU diplomats said Greek Foreign Minister George Papandreou was struggling to secure EU-wide agreement on how best to deal with Iraq.
The bloc's governments remain divided on how to tackle Baghdad.
Britain, backed by Italy and Spain, is an avid supporter of America's tough line on Iraq.
But France and Germany are still insisting on the need to avoid war against Iraq.
The six-nation meeting will be followed later on Monday by a gathering of all 15 EU foreign ministers.
In addition to Iraq, EU ministers will discuss demands for an extension of EU sanctions against Zimbabwe, including a prolongation of a visa ban against President Robert Mugabe and up to 70 other top officials.
Diplomats said France was likely to get EU approval for a visit by Mugabe to Paris in February to attend an African summit.
But in exchange, France is expected to give its go-ahead to a six-month extension of EU sanctions against Zimbabwe. The sanctions run out on February 18.
Under EU rules, the bloc's governments can waive the travel ban to allow discussions with Zimbabwean officials on democracy and human rights.
Portugal which will host an EU-Africa summit in Lisbon in April is also anxious to get a greenlight from its partners for inviting a representative from Zimbabwe to the meeting.
EU diplomats said they did not want their relationship with African countries soured by disagreements over how to deal with Zimbabwe.
But they insisted that there was no question of resuming normal relations with Harare given President Mugabe's alleged disregard for human rights and the rule of law - Sapa-DPA.
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