Arab Spring countries and the EU's southern neighbourhood are also on the agenda.
EU foreign affairs ministers’, meeting in Luxemburg this Monday (21 October), are expected to thrash out issues with the expected signature in November of the EU-Ukraine association agreement.
Analysts believe the deal will be tabled during a summit in Vilnius, Lithuania, dedicated to Europe’s Eastern neighbourhood.
One barrier in the negotiations has been the continued incarceration of Tymoshenko but this may be about to be lifted with her release expected in the coming weeks.
While her release is not a formal condition for Kiev’s progress towards the European Union, a number of EU countries – including Germany – and a number of MEPs have linked her case to the finalisation of this bilateral accord.
Some experts have warned that failing to sign the agreement with Ukraine would put in question the whole Eastern partnership ambitions of the EU.
"In case of non-signing, the Vilnius summit, instead of becoming the celebratory highlight of almost half a decade of Eastern Partnership, will be its funeral," Tom Casier from the Brussels School of International Studies told the Ukrainian Press Agency Interfax.
"The Association Agreement with Ukraine would be a major success, but it may also be the only significant one for some time to come," Casier went on.
"Armenia has withdrawn from the Eastern Partnership and doubts increasingly surround Georgia.
Political instability has even made Moldova's position in the Eastern Partnership more uncertain.
Without Ukraine it becomes very hard to see any future for the Eastern Partnership at all."
A senior EU official told journalists in Brussels on Friday that foreign ministers would discuss Ukraine at the Council meeting but that they would draw no formal conclusions at this stage.
Ministers will debate the implementation of the benchmarks that the EU set for Ukraine in December 2012, “taking into account the feedback from the European Parliament’s monitoring mission to Ukraine by pat Cox and Aleksander Kwasniewski”.
Speaking at a press conference in Luxemburg on Friday, Trade Commissioner Karel De Gucht stressed that apart from the political considerations, Ukraine also has to deliver on a number of economic benchmarks such as recycling fees on vehicles, “which are potentially in breach of its WTO commitments”.
But other Eastern partnership hopefuls are also waiting for signals from the EU foreign affairs meeting.
Moldova and Georgia both hope to initial their own association agreements with the EU at the Vilnius summit.
The EU official conceded that the ministers would focus primarily on Kiev at Monday's meeting, but he assured that the EU “does not mix Moldova and Georgia with Ukraine”, meaning that each country would be subject to a separate discussion.
Georgia will hold presidential elections only days after the Foreign Affairs Council on 27 October.
“The electoral process is satisfactory so far, let’s wait for the results of the elections and the new president, in the meantime we’ll continue to get ready for the Vilnius Summit and the initialing of the agreement,” the EU official said on Friday.
The EU Eastern partnership was launched in 2009 and covers six countries: Armenia, Azerbaijan, Belarus, Georgia, Moldova and Ukraine.
Foreign affairs ministers will also discuss the situation in the Southern neighbourhood, with a special focus on Egypt, Syria, Libya and the aftermath of the Lampedusa tragedy, as well as Myanmar, Yemen and Bosnia.
Serbia will hold its first so-called Stabilisation and Association Council with the EU in the margins of the meeting on Monday evening.
Serbia is hoping to start accession negotiations with the EU as soon as January 2014.