European Union nations have agreed to ask Serbia to sign a political deal days after the presidential election.
Mr Solana says the EU and Serbia should get closer together
The political framework agreement offers Belgrade closer trade relations and relaxed visa requirements.
EU ministers were keen to give Serbia a positive message before Sunday's election but could not agree to a full pre-membership accord with Serbia.
The Dutch government said that should wait until Serbia handed over war crimes suspects to The Hague tribunal.
Bosnian Serb General Ratko Mladic is among those indicted on genocide charges.
He is wanted in connection with the massacre of Muslim men and boys at Srebrenica during the Bosnian war in 1995.
The Serbian government says it does not know where Mr Mladic is but the EU has until now made the handover of suspects a condition of Belgrade signing the Stability and Association Agreement (SAA).
On 3 February, ultra-nationalist candidate Tomislav Nikolic takes on pro-Western incumbent Boris Tadic in the second round of the presidential election.
EU foreign ministers are inviting Serbia to sign the new deal on 7 February.
British Foreign Secretary David Miliband said "the hand of friendship is going to be extended economically, culturally, politically" to Serbia to reinforce the message that its future lay in Europe.
EU foreign policy chief Javier Solana denied that the agreement being offered to Serbia was unprecedented.
"I don't think this is absolutely new but it's important that we get the European Union closer to Serbia and Serbia closer to the European Union."
Earlier Dutch Deputy Foreign Minister Frans Timmermans insisted that the Netherlands would agree to sign the pre-membership accord "the moment Serbia hands over the people who stand indicted for the Yugoslavia tribunal".