Fiorina joins a group trying to help the star of "The Terminator" to take up his role as head of the country's most populous state. In mid-November, Schwarzenegger is expected to take over from Governor Gray Davis, who was ousted by voters in Tuesday's recall election.
In a statement on Thursday, Fiorina said she was honoured by the appointment.
"We believe a healthy business environment is critical to HP and every other California employer, large or small," Fiorina said. "The state is facing a unique and extraordinary set of challenges and opportunities that demand the involvement of all of us to address them. It's time for everyone to pull together to improve California's competitiveness."
Fiorina is not the first executive from the company to enter the political arena. Co-founder David Packard got involved in Republican politics in the late 1960s and landed a role in the Nixon administration, serving as a deputy secretary of defense. However, Packard lasted just two-and-a-half years in the post.
"To his dismay, techniques that worked beautifully at HP often proved useless at the Pentagon," journalist George Anders wrote in his book on Fiorina and HP, titled Perfect Enough.
Fiorina's father, Joseph Sneed, was named a federal judge by Nixon.
The HP executive has herself been mentioned as a potential politician one day, especially after she managed to win approval for the merger with Compaq Computer in the face of bitter opposition from the heirs of HP's founders and several of its institutional investors.
Fiorina was asked at a July event whether she would consider a career in politics, but she declined to offer a definitive answer.
"Oh, you know, anything might happen," Fiorina said at a meeting of Silicon Valley executives. "Never say never in life. It's foolish to say never. But it isn't what I'm thinking about."
Fiorina is one of 65 people named by Schwarzenegger to his transition committee. She is joined by a host of notables, including "Kindergarten Cop" director Ivan Reitman; Mayor Willie Brown of San Francisco; and Safi Qureshey, the co-founder of AST Computers. Also on the committee are former gubernatorial candidates Bill Simon and Richard Riordan, former California Governor Pete Wilson and former US Secretary of State George Schultz.
"In my campaign, I said that I would reach across the political aisle and bring the best and brightest people together to help us solve the problems facing California," Schwarzenegger said in a statement. "The Transition Committee I am announcing today is a distinguished group of men and women who share my commitment to restoring California to greatness."
Last month, Fiorina stepped down as a director of networking-gear maker Cisco Systems.
