The 62-year-old faces fraud and criminal group offences over his alleged role in the scam, which convinced the women to hand over money and valuables to be "blessed".
They were told not to open bags meant to contain their valuables, which the alleged fraudsters had switched out.
NSW Police say it's the work of a "fly-in, fly-out" criminal syndicate.
The scammers typically come to Australia from China for short stints to carry out the fraud, convincing older women that their money and belongings needed to be "blessed" to avoid bad luck, police claim.
The man was arrested on Friday at Brisbane Airport and extradited to Sydney on Tuesday.
This follows the arrest of a 63-year-old woman at Sydney Airport on Thursday night.
Detective Superintendent Guy Magee said the scammers typically targeted older Asian women, exploiting cultural superstitions.
"They will convince them to go and speak to a spiritual healer, to go to their home and retrieve their life savings, all their jewellery," he told reporters following the woman's arrest.
The alleged scammers convince victims that items in a bag have been blessed and tell them not to open it or they will face "bad fortune".
"Unfortunately, the victims are opening those bags to find their money and jewellery is simply not in there," Det Supt Magee added.
More than 50 individuals are believed to be connected to the scam across the east coast of Australia, with 11 arrest warrants issued.
Police have received reports of more than 80 incidents across Sydney since 2023.
They are trying to find a further seven people believed to be involved in the syndicate.
The scams are believed to have netted $3 million in cash and valuables.
Police have warned people to not hand over money or jewellery for blessing rituals.
Others have been urged to keep watch on older family members with limited English and warn them they could be targets of the scam.
The man will appear in Downing Centre Local Court on Wednesday.
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