The trio were arrested after dozens of heavily armed police swooped on the six properties about 6.15am, seizing five firearms, including four handguns and an assault rifle, various calibres of ammunition, illicit drugs and steroids.

Police say the raids came after a five-month operation in which an undercover officer allegedly bought 13 firearms from the ring including pistols, two shotguns, seven revolvers and a rifle and thousands of rounds of ammunition.

Detectives attached to Strike Force Bootle seized a further five guns on Tuesday, bringing the total to 18.

The group's alleged kingpin, drummer Paul DeMarco, 55, is charged with 27 firearm offences and bowed his head and snorted during a brief appearance at Blacktown Local Court on Tuesday.

The Windsor man will remain in custody until his court appearance on Wednesday where it is expected he will make an application for bail.

DeMarco performed with the Angry Anderson-led Rose Tattoo between 1992 and 1993 before rejoining in 1998 and recording on their three most recent albums.

Ibrahim, brother of Kings Cross identity John Ibrahim, appeared more concerned about not having shoes rather than the charges he was facing.

A police officer involved in his arrest promised his shoes would be given back to him once he was inside Penrith Police Station.

"I've got bad feet, I've got to f---ing put them on man," Ibrahim said.

"We won't make you walk without them," a female officer replied.

The 45-year-old, from Greystanes, was charged with five offences involving the sale of firearms and possession of steroids.

Wearing a green tracksuit jumper, blue jeans and the white sport shoes he so badly wanted to wear, Ibrahim bowed his head and thanked the magistrate after he was formally refused bail. He will next appear in court on April 9.

His sister, Jazz Dior, 43, of Wentworthville, was arrested in Warilla and taken to Oak Flats Police Station where she was charged with conspiracy to supply a firearm to a person unauthorised to possess one.

Dior was formally refused bail at Wollongong Local Court. She will reappear on April 3.

Assistant Commissioner Denis Clifford said the operation, led by Penrith detectives, had made a "significant dent" in the sale of illegal firearms.

"When you look at them [the weapons] you shake your head and wonder what that firepower would do if it fell into the wrong hands," he said.

"There is always that chance, always that possibility that an innocent bystander will get shot.

"Our allegations will be that these weapons were sold with the ammunition to go with it. So ready for use."

He expects more arrests over the alleged syndicate.

Customs have been contacted as part of the investigation.