Brown's execution was scheduled for 12:01 a.m. Wednesday. It is the state's first execution in nearly five years. It was not immediately clear why the governor choose a 45-hour time frame.
The delay means Brown is now scheduled to die by lethal injection at 9 p.m. Thursday.
Corrections officials said the governor said the delay is to allow the appeals courts time to weigh in on the case and give him time to consider a clemency request.
The legal twist by Schwarzenegger was the latest in a series of back and forth volleys.
Earlier Monday, a judge in Marin County Superior Court refused to block Brown's execution after he argued in a lawsuit that California's new death penalty regulations were improperly adopted.
"Mr. Brown cannot prove that he will suffer pain if he is executed under the current regulations," Judge Verna Adams said.
The ruling was similar to one on Friday out of a San Jose court. There a judge ruled against the accused contension that California's lethal injection process put him at risk of suffering cruel and unusual punishment.
Brown's attorneys have now turned to state and federal appeals courts in their bid to stop the execution of Brown, who was convicted of abducting, raping and killing a 15-year-old Riverside girl on her way home from school in 1980.
Attorney General Jerry Brown's office also got in the mix. It suspended all executions after Sept. 30 because of a drug shortage.
It turns out the state is going to run out of one of the three drugs used in its lethal injection process by the end of the month and were unsure when they would receive a new supply.
The Associated Press reported Hospira, the only company in the country that makes the drug, said it has production problems and can't deliver any new shipments until early next year. Several other states have rescheduled executions because of the drug shortage.
Hospitals use the drug as part of the process to induce anesthesia but they are not allowed to give any of the chemical to prisons.
The governor's time frame of a Wednesday evening execution would still happen in the month of September, so this could still happen.