Dan Senor replaces Cindy McCaffrey, who stepped down as V-P of corporate marketing late last year. His job will be the top communications post.
Senior manager of corporate PR Steve Langdon confirmed that Senor had joined the company but declined to provide further information. Senor was not available for comment.
Speculation in Silicon Valley was that Google had been looking to make an unconventional hire for the position.
In addition to his role as spokesman in Iraq, Senor was a senior adviser to Paul Bremer, administrator of the Coalition Provisional Authority (CPA).
Senor's post was dissolved, along with the CPA, after the US transferred power to an interim government in June last year.
During 'Operation Iraqi Freedom', Senor served as director of the coalition information centre, based in Qatar. He has also served as a legislative aide, press secretary, and communications director for former Republican senator Spencer Abraham.
Senor joins Google as competition among search engines intensifies. Microsoft and Yahoo! are looking to challenge Google's dominance, and search companies are adding new functionality to differentiate their services, from hotel listings to search software for mobiles.