Javier Solana, the EU foreign policy chief, was to open the talks on Monday with a working dinner, to be followed by another meeting on Tuesday morning.
Nine EU countries and 12 member states of the Arab League are being represented at foreign minister level at the talks, including Spain, Italy, Ireland, Egypt, Jordan and Saudi Arabia.
Slovenia, the current EU president, is co-chairing the talks along with Saudi Arabia and host Malta.
Frendo launched the initiative for the talks in September 2006 with a letter to the then-Finnish EU presidency.
Slovenia has described the meeting as "a unique and highly opportune event, as dialogue with Arab partners is currently of vital importance in view of the current regional and global challenges in world politics."