Williams, a youth center counselor, was reportedly on his way to pick up his paycheck at the time.
Baldwin Park police said they spotted a blue sport utility vehicle that had been reported stolen in El Monte earlier in the morning.
They ordered the driver, 28-year-old Luis Noriega, to pull over, but the suspect took off and led police on a high-speed chase.
"The pursuit was short, approximately two and a half miles," said Baldwin Park police Lt. David Reynoso. "During the pursuit when the vehicles reached the intersection of Ramona and Francisquito in the city of Baldwin Park, the suspect vehicle collided with a second uninvolved motorist."
Williams was ejected from the vehicle and pronounced dead at the scene. His vehicle burst into flames.
"I looked out the window and the car was all in flames, the whole car not the front, not the back but the whole car," said Cristine Sanchez. "There's no way that person was safe."
Noriega managed to get out of the SUV and ran from the crash scene, but was later caught and taken into custody.
He is under arrest on suspicion of murder, evading police and grand theft auto.