Assembly Bill 4, dubbed the Trust Act, prohibits local law enforcement agencies from detaining people for deportation if they are arrested for a minor crime and otherwise eligible to be released from custody.
He also approved a bill that allows lawyers to be admitted to the California bar, even if they're in the U.S. illegally.
Another bill Brown signed allows community colleges to exempt pupils attending as special part-time students, from paying nonresident tuition.
The news comes days after Brown signed into law a bill granting driver's licenses to immigrants lacking legal immigration status.
Hundreds of immigrants and supporters marched Saturday through Hollywood as part of nationwide rallies to push for immigration reform as California's governor signed a series of bills on the topic.
"While Washington waffles on immigration, California's forging ahead," Brown said. "I'm not waiting."
The Associated Press contributed to this report.