Mr Schwarzenegger said he wanted to waste no time in the clean-up |
He has ordered all available resources to be deployed to tackle the 58,000 gallon (228,000 litre) spill, which is putting wildlife and beaches at risk.
The spill occurred on Wednesday, when a tanker struck the San Francisco Bay Bridge, and is said to be spreading.
Some critics have reportedly questioned the speed of the initial response.
The governor's office said special "skimmers" and booms were being used to try to recover some of the oil and limit the slick's spread.
Mr Schwarzenegger said he had signed the emergency order so that the clean-up operation could progress "without wasting a minute of time".
The spill is reportedly the largest to affect the San Francisco Bay area since 10,000 gallons of fuel leaked from a ship undergoing repairs in 1996.
The California department of fish and game has reported finding two dozen sea birds covered in oil and has said hundreds more may be at risk.
The agency's assistant chief Steve Edinger told the AFP news agency the spill was a "very significant event".
No more fuel is now leaking from the Cosco-Busan container ship that caused the spill.
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