If formally signed in November, it would be the EU's furthest-reaching treaty with a country not currently negotiating membership.
EU ministers have said the deal is dependant on Kiev introducing extensive reforms, and are urging the release of opposition leader Yulia Tymoshenko.
The move also takes place against strong objections from Russia.
Prime Minister Mykola Azarov described the deal as a decision of historical significance - Ukraine's roadmap to a strong economy and high standards of living.
"We all want clean air and water, safe food, good education for our children, up-to-date medical services, reliable legal representation.
"All these are not abstract terms, but norms and rules that are already in place in the EU," Mr Azarov told ministers.
Russia, which ruled Ukraine for centuries until 1991, has said if the association agreement is signed its markets could be flooded with less-expensive European goods, and warned it could take retaliatory action.
Russia is pushing Ukraine to join a Kremlin-led customs union with Belarus and Kazakhstan.
Russian President Vladimir Putin hopes to establish a "Eurasian Union" - a trade bloc similar to the EU, but without the commitments to democratic values and open competition which are fundamental to EU membership.
Last week, the EU's commissioner for enlargement, Stefan Fuele, issued a warning to Moscow, saying it was "unacceptable" to use threats against ex-Soviet states.
Mr Fuele's words came after Russia banned imports of Moldovan wine and spirits, citing quality concerns.
The European Commission - the EU's executive - is hoping to clinch association agreements with Moldova and Armenia in November.
Ukraine's strategic importance for Russia historically far outweighs that of Armenia or Moldova, and Ukraine's heavy reliance on Russian gas has given Moscow considerable leverage.
Russia's gas monopoly Gazprom has previously cut supplies to Ukraine in the winter, complaining of overdue bills.
Source: BBC News