The 53-year-old was arrested at her home in Vincentia, south of Nowra, at 7.20am on Wednesday morning.
The home was raided by officers, who seized electronic devices and documents for forensic examination.
The woman was taken to Nowra Police Station and charged with 749 counts of dishonestly obtain financial advantage by deception.
Police will allege in court that the woman misappropriated money from a number of accounts connected to the family business totalling more than $1.5 million over a decade.
She was granted conditional bail to appear at Nowra Local Court on Monday, April 26.