Sixty-five-year-old John Sidney Denham was yesterday charged with 30 child sex offences relating to boys aged 11 to 17 in the 1970s and early 1980s.
Sixteen of Denham's alleged victims attended St Pius X High School at Adamstown. Another boy was from a parish near Newcastle, while the 18th was from Taree.
Detectives were tipped off by the Catholic Church's child protection unit in April.
Acting Police Commander Gary O'Dell has hinted further arrests could follow.
"We're certainly looking at a number of further allegations and making inquires in relation to that," he said.
"As far as the likelihood of a timeframe of any further arrests, that's something I can't comment on at this stage.
"The police have been working with a number of victims and if there are any others out there, we would certainly encourage them to come forward."
Denham also worked at Sydney's Waverly College during the 1980s and 1990s. None of the charges relate to his time there.
He was on restricted duties and working next to a Sydney school as a librarian at a theological college before being arrested yesterday.
The priest has been remanded in custody and will face Newcastle Local Court on October 2.
The Maitland-Newcastle Catholic Diocese says it will continue to cooperate with the police investigation.
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