- The Terminator star was, along with Bruce Willis, Demi Moore, Sylvester Stallone and Whoopi Goldberg, one of the public faces of the Florida-based company, which has nearly 80 restaurants worldwide.
Schwarzenegger said he was ending his five-year contract with the company - which filed for bankruptcy under US law last year - to concentrate on his film career and other business ventures.
"It was lots of fun and very challenging to come up with and develop the celebrity restaurant concept on an international level," he said in a statement.
"Of course, I am disappointed that the company did not continue with the success I had expected and hoped for."
The company emerged from bankruptcy last week, when chairman and chief executive Robert Earl announced a fresh injection of funds from majority investors into the chain, which would concentrate on boosting trade at its existing restaurants, rather than opening new outlets.
He said the company's rush to expand around the world had caused its financial problems.
Mr Earl also said a new line-up of celebrity endorsements would be announced in the next three to four weeks, which would help it appeal to younger customers.
A company spokeswoman said that the chain would still be able to use Schwarzenegger memorabilia in its restaurants, and that as far as it was aware, other celebrities associated with Planet Hollywood were still backing the chain.
A spokeswoman for Schwarzenegger said his decision to pull out had nothing to do with Robert Earl's plans for the future of the chain he helped found in 1991.