Brown vetoed a broader measure in 2012 that critics said would possibly lead to government regulation of part-time baby-sitting.
The new law takes effect in January 2014. Domestic workers must be paid time-and-a-half if they work more than nine hours in a day or more than 45 hours in a week. Baby-sitters are exempt from the mandate.
The overtime requirement will end in January 2017 unless renewed by the Legislature.
Labor groups say domestic workers, who tend to be female immigrants, often are not protected under labor and employment laws. California is the latest state to offer certain protections, after New York and Hawaii.
New federal rules approved last week would extend minimum wage and overtime laws to home health care workers starting in January 2015.
Some employers and groups representing home care workers, such as the California Association for Health Services at Home, opposed the California measure. They say the overtime-pay requirement will raise the cost of care, which will be a burden on families whose insurance plans do not cover home care services.
The legislation also requires the governor to appoint a committee composed of workers and their employers to report on the law's effects.
The Associated Press contributed to this report.