The surprise choice of German Defence Minister Ursula von der Leyen to replace Jean-Claude Juncker came after the main front-runners were rejected.
IMF chief Christine Lagarde has been nominated as the first woman to head the European Central Bank (ECB).
The announcement follows days of difficult negotiations.
In all, EU leaders were tasked with nominating five people for the top jobs.
Belgian liberal Prime Minister Charles Michel is nominated to replace European Council President Donald Tusk while Spain's Josep Borrell is proposed as foreign policy chief.
The fifth key role - president of the European Parliament - is to be chosen on Wednesday. Possible candidates include German centre-right MEP Manfred Weber and Bulgarian socialist Sergei Stanishev.
Most of the roles must be ratified by parliament.