Once member states and the European Parliament have given their approval, Tuesday's decision will remove duties on agricultural products, processed foods, textiles and industrial goods, saving Ukrainian businesses 487 million euros a year.
In total, it will mean preferences being granted to more than 80 percent of Ukraine's exports, giving the country of 46 million people nearly full and open access to the European Union's market of 500 million consumers.
Once presidential elections have been held in May and a new government formed, the EU will also sign a free-trade deal with Ukraine, completing the "association agreement" that was rejected by former president Viktor Yanukovich last November, leading to months of protests and his overthrow.
As well as steps to prop up Ukraine's economy, the EU is trying to apply pressure on Russia to withdraw forces from Crimea and limit its influence in the east of Ukraine.
It has already cancelled negotiations with Moscow on visa cooperation and a trade and investment pact, and is now preparing sanctions including asset freezes and travel bans.
(Read more: Why Ukraine's bailout money could end up in Russia)
Those steps could be agreed by EU foreign ministers at a meeting on Monday, unless Moscow takes clear steps to reverse course and engage in direct talks with the interim Ukrainian government on ways to end the crisis.
Senior officials from the United States, Italy, France, Germany, Poland and several other countries were meeting in London on Tuesday to coordinate the targeted measures to be taken against Russia if it does not respond.
"You can expect the focus very much to be on (Russian) officials who have links to the action that's being taken with regard to the violation of Ukrainian sovereign territory," Prime Minister David Cameron's spokesman said.
Officials said, however, that any EU travel bans or asset freezes were unlikely to target Russian President Vladimir Putin or his foreign minister, Sergei Lavrov, at least not initially, so as to keep channels of communication open.
But as well as sanctioning Russia, the minds of EU officials are focused on supporting the Ukrainian economy, especially as the country is now being put on track to more fully integrate with the 28-nation union. While membership may not be on the cards, the EU wants to ensure Ukraine doesn't collapse.
"The idea is for the EU to open its doors to export from Ukraine, helping to give a real boost to Ukrainian businesses with a real impact on daily lives," said De Gucht.
"I would now encourage the European Parliament and the Council to fast track the approval process so the tariff reductions can be in place by June."