He will appear in Bankstown Local Court on Friday after he was refused bail by police.
Mr Oluwafemi's arrest comes after three other alleged syndicate members were apprehended by police under Strike Force Woolana.
Police arrested 36-year-old Nigerian national Harriette Bangura last Tuesday and charged her with laundering $500,000 that police allege she obtained through fraudulent business emails.
Officers have since seized a Land Rover suspected to be the proceeds of crime, as well as mobile phones, documents and SIM cards from her Kingswood home and a Hoxton Park storage unit.
She was charged with 11 counts of dealing with the proceeds of crime and was granted bail by Central Local Court to reappear in November.
Officers also raided a Chester Hill home last Wednesday and arrested two other Nigerian nationals for their alleged roles in the scam.
A 20-year-old man, who police say helped launder $90,000 through fraudulent business emails, was arrested at home and charged with seven counts of recklessly dealing with the proceeds of crime and an identity theft offence.
A woman, also 20, was charged with knowingly dealing with the proceeds of crime. Police will allege that she was involved in the laundering of $17,000 obtained through business email compromise.
Cybercrime Squad Commander, Detective Superintendent Arthur Katsogiannis, said people needed to be vigilant.
"While there are many variables, generally, the perpetrators will 'spoof' or compromise corporate executive or employee email accounts and send email requests to an accounts payable employee for an electronic funds transfer," he said.
"Staff should be suspicious about these types of requests, and if they take the time to verify the authenticity of the email, whether it be via phone or a fresh email, they can potentially prevent the compromise."
Australian Border Force detention operations commander Bill Ries said the incident proved detainees should not be allowed access to mobile phones.
"We know phones can be used to co-ordinate escape efforts, as a commodity of exchange, to facilitate the movement of contraband, to convey threats and, in this case, to organise significant criminal activity outside our centres.
"The continued use of phones in detention poses a significant threat to our staff, to detainees and the broader community."