Democrat Fred DuVal has made his candidacy for governor official, as one of only two Dems whose names have been tossed around in the media for the seat in 2014.
DuVal has a lot of titles you could use to describe him, like former underling to President Clinton and Governor Bruce Babbitt, lobbyist, unsuccessful congressional candidate, and Arizona Board of Regents chairman. (His campaign appears to prefer "business and education leader.")
It seems insanely early to talk about an election that's taking place well over a year from now, but DuVal seems to be the first person to make a run official, and he's already got a pretty good list of endorsements ("good" being a relative term, as Arizona's a little weak in the Democrat department).
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House Minority Leader Chad Campbell is the only other Democrat whose name has been associated with a gubernatorial run.
On the Republican side, Governor Jan Brewer has repeatedly insisted that she can run for an unconstitutional third term, which she cannot.
Secretary of State Ken Bennett, Treasurer/ice-cream man Doug Ducey, Mesa Mayor Scott Smith, ex-Tempe Mayor Hugh Hallman, and state Senator Al Melvin are reportedly considering runs for governor, too.