Wednesday's announcement comes about two months after DuVal announced the creation of a formal exploration committee. Since then, he has collected a large number of endorsements from prominent Democrats.
Democratic Representative Chad Campbell has also signaled interest. He is the House minority leader.
On the Republican side, former Tempe Mayor Hugh Hallman has entered the 2014 governor's race, while other possible candidates include Secretary of State Ken Bennett, state Treasurer Doug Ducey and Mesa Mayor Scott Smith.