EU External Relations Commissioner Benita Ferrero-Waldner said the assistance will focus on strengthening "good governance and democratic institutions" in Ukraine.
It also is aimed at helping bring Ukrainian legislation closer into compliance with EU standards.
On March 5, Ukraine and the EU began negotiations on closer economic and political ties. They are working on a new cooperation agreement to replace a current version that expires in 2008.
But the EU stopped short of recognizing Ukraine as a candidate for membership.