The 31-year-old was charged on Sunday with 11 offences, including two counts of dangerous driving occasioning death and other driving offences, after he allegedly led police on a frenetic chase through Sydney streets.
The man allegedly began the rampage by punching a 25-year-old man in the face and stealing his red sedan at a petrol station in South Hurstville at about 10.20am on Saturday.
He failed to stop for highway patrol officers in Beverly Hills minutes later, prompting a large-scale police chase.
Police chased the driver along the M5 motorway while the police helicopter tracked him.
The pursuit was called off in the Bankstown area about 10.30am.
"He was driving in what I could describe as one of the most reckless and dangerous demonstrations of driving I've seen in a long time,' Assistant Commissioner Brett McFadden said.
"He was overtaking vehicles at speed in the breakdown lanes, he was crossing over to the incorrect side of the road. All of which without police vehicles around him."
The 31-year-old was tracked by air for at least 40 minutes before he crashed into an Alfa Romeo sedan on the Old Hume Highway in Camden South about 11.10am.
"The offending driver has gone up the inside of those vehicles at speed, crossed into the intersection and impacted with another vehicle that had the lawful opportunity to turn right," Mr McFadden said.
A 60-year-old woman driving the Alfa Romeo and an 84-year-old female passenger died at the scene.
The pair are part of an extended family.
The circumstances surrounding the crash have been declared a critical incident and will be investigated by the police watchdog.
A second probe will be launched into another police pursuit that ended in serious injury in southwest Sydney on Saturday night.
Officers attempted to stop an e-bike rider who was allegedly riding without a helmet about 11pm.
The 39-year-old crashed into a pole and was taken to hospital with serious injuries after allegedly continuing to ride past police.
Investigations into both crashes will be reviewed by the Professional Standards Command and overseen by the Law Enforcement Conduct Commission.