"We hope to go on further (on) normalizing our relations with Libya. Our relations with Libya were to a large extent blocked by the non-settlement of this medics issue," Barroso told reporters.
He said the 27-nation bloc could move to include Libya in regional trade and aid ties with other Mediterranean countries. The EU is also keen to cooperate closely with Libya on migration issues.
Barroso said EU External Relations Commissioner Benita Ferrero-Waldner had reached agreement with Libyan authorities on a "memorandum" which aims to develop closer EU-Libya ties as part of a wider agreement that secured the freedom of the medics after eight-and-a-half years in prison there.
The medics, who were sentenced to life in prison on charges of contaminating children with the AIDS virus, arrived home to Sofia, Bulgaria, Tuesday morning on board a plane with French first lady Cecilia Sarkozy and Ferrero-Waldner.
She said in a statement the deal with Libya "will open the way for a new and enhanced relationship between the EU and Libya."
Barroso and other EU officials praised Ferrero-Waldner and Sarkozy's role in getting a final deal to release the medics.
"As you know we have been working very hard to solve this dramatic situation and we are very happy to see the outcome," Javier Solana, the EU's foreign policy chief told The Associated Press.
"We hope this will be another element to turn a new page with Libya, and I'm looking forward to that," he said.
Barroso said Libya could "expect progress in different fields" of cooperation like trade, energy, migration and other policy areas. It was not clear if Ferrero-Waldner offered Libya economic aid as part of the agreed to package to better ties.
Tuesday's EU gesture marks another step toward improving ties with Libyan leader Moammar Gadhafi after the EU ended 12 years of sanctions against his North African country and eased an arms embargo in 2004 to reward the country for giving up plans to develop nuclear weapons.
The sanctions were also dropped after Libya handed over two nationals indicted for the 1988 bombing of an American Airlines plane over the Scottish town of Lockerbie.
Relations remained tense between the EU and Tripoli over the conviction of the five Bulgarian nurses and a Palestinian doctor accused of deliberately infecting more than 400 Libyan children with the AIDS virus.
The Europeans are eager to invest in Libya's substantial oil reserves and obtain its cooperation in stopping the flow of illegal immigrants into Europe.
As a sign of warming relations, Gadhafi visited the EU's Brussels headquarters in April 2004 on his first trip outside the Mideast or Africa in 15 years.
EU officials have also tried, without success, to get Libya to sign up to an EU aid and trade pact it has with North African and Middle Eastern nations.
To join up to that pact, Libya will have to sign declarations renouncing terrorism as well as committing to implement democratic reforms and respect human rights, something it has so far refused to do.