The summit is set to be the first of its kind since Kiev signed an Association Agreement with the European Union last year.
President Poroshenko and European Council President Donald Tusk are expected to discuss the implementation of the agreement as well as ongoing efforts to bring an end to the year-long armed conflict in Ukraine's east.
European Commission President Jean-Claude Juncker and Johannes Hahn, the union's Enlargement Negotiations Commissioner, are also due to attend the meeting.
During the talks, President Poroshenko could reiterate his calls for UN peacekeepers to be deployed in the country to enforce the ceasefire that Kiev signed with the self-proclaimed republics of Lugansk and Donetsk in mid-February.
The Ukrainian and EU leaders could also discuss the free trade zone, scheduled to come into effect next year. A possible visa-free regime between the European Union and Ukraine, as well as financial aid to Kiev could also be on the agenda of the talks.
The current Ukraine-EU summit is seen as part of preparations for the Eastern Partnership summit that will bring together EU officials with representatives from six former Soviet republics, including Ukraine, in Latvia next month.