Authorities identified the twins as Timothy and Thomas Espinosa. The 48-year-old brothers were spotted by police at a motel near a Chevron gas station.
When the suspects left the motel around 5:30 p.m. Thursday, police followed them.
"They attempted to stop the car. One of the suspects fled from the car, he went around the backside of the Chevron station. Officers went around the front and that's when the officer-involved shooting occurred," Cpl. Anthony Bertagna said.
The intersection was shut down until about 2 a.m. Friday. Neighbors were trying to figure out what happened when they heard the shooting.
Authorities said the Espinosa twins are responsible for eight armed robberies in Santa Ana that happened in April until a couple of days ago. Five of those robberies were committed at Metro PCS stores.
"They're violent people and fortunately they're now off the streets because of our going to the media and the community coming forward and helping us get these guys identified," Bertagna said.
Thomas Espinosa was booked into jail on suspicion of multiple counts of robbery and kidnap for robbery. His brother, Timothy, was the one shot during the police shooting and will be booked on multiple counts of robbery when he is out of the hospital.
Authorities said one of the twins has spent at least 20 years of his life in state prison.