Tolls will be capped at $60 a week under an election pledge by Labor, which is hoped to bring cost-of-living relief to more than 50,000 drivers.
The toll cap would be in place for two years and will commence on January 1, next year.
The $150 million plan comes ahead of the state election, which will be held on March 25.
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Opposition Leader Chris Minns said the cap, which will be administered by Service NSW, would be on top of the existing toll rebate and M5 cashback schemes.
"Under Labor, motorists get more and better toll relief," he said.
Professor Allan Fels, former chairman of the Australian Competition and Consumer Commission (ACCC) will also lead an overhaul of the toll network.
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Last month, NSW Premier Dominic Perrottet announced his government would give the toll system a major restructure by 2025.
He said the restructure would result in drivers paying less to use Sydney's motorways.
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