Sort of tongue in cheek. Couldn't fill them all in, but I got a couple. Only two serious ones though.
Vice President: Ross Perot
Department of Defense: John McEnroe
Department of Education: Paula Roundstone
Department of Energy: Kenneth Lay
Department of Homeland Security: Major General Harold Mashburn Jr. -Serious
Department of the Interior: Scott Ritter -Serious
Department of Justice: Clint Eastwood
Department of Transportation: Andre Hakim
Department of the Treasury: William Buffet
Department of Veteran Affairs: Jack Nicholson
EPA: Phillip Morris
Office of Management and Budget: Bill Gates
Office of National Drug Control Policy: Ron O'Neal
U.S. Trade Rep.: Christopher Walken
Chief of Staff: Collin Farrel