Tina Montana, 47, was arrested in Punchbowl, in Sydney's southwest, on Wednesday as NSW Police seized a stack of items linked to the allegedly shonky readings operation.
They included a crystal ball, divination cards and small, antique statues.
Two other people known to the woman have previously been charged in relation to the scheme, which police allege has been operating across Sydney since as early as 2006.
Police allege the syndicate members were purporting to be psychics in a ruse to defraud their victims out of money and other property.
Montana, a dual British-Australian national, was charged with 13 offences including seven counts of identity theft, after being accused of using multiple stolen identities to create phone accounts.
One of her three money laundering charges pertained to a 2018 event where she allegedly bought a $54,000 gold bar and smuggled it into England.
Police arrested a woman in Punchbowl over alleged fraud. (Supplied by Nsw Police/AAP PHOTOS)
Montana's sister and her partner face a number of obtaining financial advantage by deception charges, with Montana accused of being a part of their criminal group.
Detective Inspector Craig Brooks accused the group of targeting their victims for financial gain.
"Police will allege the syndicate were claiming to be psychics and during that process with the victims they were encouraging them to provide them with property and money, which they have obviously kept," he said.
"(They have) not returned it in breach of what the victims would have expected when engaging these services ... these matters have caused significant financial and emotional distress."
Detectives have been investigating the so-called psychics since July.
Asked about allegations those charged were taking money to "spiritually cleanse" it, Det Insp Brooks confirmed that possibility would form part of the investigation.
Some of the tarot and other divination cards seized by officers working on the case. (Supplied by Nsw Police/AAP PHOTOS)
"Clearly, if any person out there is asked to provide money to any psychic for any services, I strongly urge them not to," he said.
Montana was denied bail at the Bankstown Local Court on Wednesday, with Magistrate Glenn Walsh finding no special circumstances to grant her release.
After arresting the two other alleged offenders earlier in November, police searched a storage unit in Chatswood, on Sydney's lower north shore.
Items they seized included antique statues and a sword, a crystal ball and WWII collectors' memorabilia.
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