He was issued a Court Attendance Notice for the offence of engage in relationship with inmate cause safety risk to correctional centre.
The man was granted strict conditional bail to appear at Burwood Local Court on November 25.
NSW Police took over investigating relationships between inmates and guards after the legislation was introduced.
"Any inappropriate relationships identified at correctional facilities across the state will be brought to the attention of police and charges will be laid," Detective Inspector Robert Hollows from the Corrective Services Investigation Unit said.
The new legislation regarding guards and inmates was passed in November last year and came after a number of female guards allegedly had sexual relationships with prisoners.
If convicted of the crime, public and private correctional officers can be sent to prison for up to two years and/or receive a fine of up to $2200.
Prior to the passing of the bill, such relationships were against prison codes but weren't illegal, let alone a crime.
Minister for Corrections David Elliot told radio host Ray Hadley in July he was going to "fix" the issue.
"It's an insult to the victims of crime, which is why I've started the process to increase the penalties for any officer found having a sexual relationship with an inmate," Mr Elliot said.
"As far I'm concerned, if I can't pull that off I've got no business being in cabinet.
"I have made it very, very clear to all and sundry in the last 24 hours that this is non-negotiable as far as I'm concerned.
"If I have some smart lawyer or bureaucrat tell me otherwise, well then, there's going to be a stand down."
