The Sydney man's arrest is the latest in a string of busts targeting a group that allegedly used stolen personal information to apply for loans to buy non-existent luxury "ghost cars".
The 36-year-old was hit with 19 charges after he was arrested in the city's southwest on Thursday.
NAB, who worked with NSW Police on the matter, confirmed the man's employment had been terminated, adding the bank had zero tolerance for criminal conduct.
No customers had been impacted by the alleged fraud, it confirmed.
The man was the 15th person charged by a NSW Police strike force targeting the same syndicate, while the NSW Crime Commission has seized $60 million in assets.
Police allege the man used his position at NAB to help the syndicate apply for approximately $10 million in business loans.
The syndicate was initially accused of using the stolen personal data to get loans to buy luxury cars that didn't exist, but the investigation has since widened and now alleges the group also took in money from fraudulent personal, business and home loans.
NAB's group investigations executive Chris Sheehan said the bank acted swiftly to investigate and sack the accused.
"NAB has worked in partnership with NSW Police on this matter and continues to provide significant support to aid the investigation and attempted recovery of any funds lost to criminal activity," he said.
"There is absolutely no place for financial crime in our community and we recognise the important role we play in the monitoring and reporting of suspicious activity, working closely with police as well as regulators and government agencies as necessary."
The man was charged with nine counts of dishonestly obtaining financial advantage by deception.
He was also charged with participating in a criminal group, dealing proceeds of crime charges and possessing anabolic steroids.
The man will appear in Fairfield Local Court on Friday.
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