Over 50,000 drivers would be better off under the plan, saving around $147 million over its initial two year lifespan, the party said.
Professor Allan Fels, renowned economist and former chair of consumer watchdog the ACCC, would be appointed to lead the review of the state's toll system under Labor.
Opposition leader Chris Minns said deals made by the current government were driving record tolls.
"This mess is Dominic Perrottet's own making - they have signed secret contracts and privatised toll roads," Mr Minns said.
"Toll companies can't lose, Sydney drivers can't win."
The change would be on top of the government's existing rebate of up $750 for eligible drivers and M5 cashback scheme.
Prof Fels would lead a review into long term reform options to overhaul the tolling system in NSW, including reviewing contracts with private road operators, the biggest of which in Sydney is Transurban.
A cap of $60 a week would commence on January 1, 2024 if Labor wins the March election and any tolls charged above the cap would be refunded on a quarterly basis by Service NSW.
Last week private operator Transurban, which controls 10 out of 12 of Sydney's tolls roads, said the state's drivers paid over $835 million in tolls in just six months.
In a note to investors the company revealed earnings of $1.66 billion for the back half of last year and said tolls would increase by around 20 per cent over the next four years.
The government has conducted a review of Sydney's tolling system, which was due for completion last September, but has been delayed for release until after the election next month.
