Governor Gavin Newsom's office Monday said he was signing the order ahead of his State of the State speech on Tuesday.
"The border 'emergency' is a manufactured crisis," according to excerpts of the speech sent to AFP by his office.
"And California will not be part of this political theater."
Newsom's office said most of the 360 troops deployed at the US-Mexico border will be redeployed to focus on "the actual threats" facing the western state, such as wildfires.
Trump argues the troops, who are supposed to provide surveillance and assist border agents, are needed to fight illegal immigration. The troops cannot act to enforce the law or to make arrests.
Newsom's predecessor, Jerry Brown, also a Democrat, last April approved the deployment of California National Guard troops but vowed they would not take part in any mission to build Trump's long-sought border wall or to enforce federal immigration laws.
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