The Democratic governor named Jeffrey Beard, 65, as secretary of the California Department of Corrections and Rehabilitation.
Beard oversaw a much smaller department as corrections secretary in Pennsylvania from 2001 until he retired in 2010, serving under both Republican and Democratic governors.
Brown said Beard has the experience California needs.
"In the face of a plethora of Federal court decisions and the bold realignment enacted by the Legislature, Jeff Beard has arrived at the right time to take the next steps in returning California's parole and correctional institutions to their former luster," Brown said in a statement announcing the appointment.
The position pays $225,000 a year and requires Senate confirmation.
California has about 133,000 inmates and more than 46,000 employees but is reducing the size of both as it tries to cut costs and reduce the population in crowded prisons to comply with federal court orders.
A 2011 law Brown approved has been sending less serious offenders to local jails instead of state prisons, leaving behind a more violent inmate population.
In Pennsylvania, Beard oversaw about 51,000 inmates and 16,000 employees, but he also is familiar with California's prison system and has helped guide many of its recent changes.
He was a member of an expert panel in 2007 that advised California prison officials on ways to improve their prison and parole programs and has been a consultant for California's prison system since 2011 as it works to improve mental health treatment for inmates. In those roles, he already has visited many of California's 33 adult prisons.
Beard is a licensed psychologist who has master's and doctorate degrees in counseling. Since he retired, Beard has advised state agencies, private companies and the National Institute of Corrections on corrections, security and mental health issues.
Prison officials said he was not available to comment on Wednesday. He issued a statement saying he is honored by the appointment.
Beard replaces Matthew Cate, who resigned last month to become executive director of the California State Association of Counties. Cate served 4 1/2 years under Brown and his Republican predecessor, Arnold Schwarzenegger.