Police allege the men - aged 37 and 57 - went on a stealing spree between Saturday and Wednesday, accusing them of running the scam 18 times at shopping centres across NSW.
The scheme, which authorities said was aimed at elderly women drivers, allegedly involved one man approaching a victim and informing them there was an issue with their car while encouraging them to open the bonnet to have a look.
Their offsider would then go through the inside of the car and plunder wallets, purses, cash and cards, police said.
The duo were arrested in Glenthorne, near Taree on the NSW mid-north coast, on Wednesday.
Police said a search of the pair and their vehicle found $6000 in cash, passports, mobile phones, a laptop and a number of money transfer receipts.
They are accused of targeting a wide span of NSW shopping centre car parks, including in the Sydney area along with Goulburn, Newcastle and Wagga Wagga.
The pair have been hit with 72 charges each relating to theft, fraud and entering a vehicle without consent.
Each will face Bail Court on Thursday.
Police are chasing another two men they would like to speak to in relation to the incidents, both described as caucasian men in their 40s.
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