Arthur Psichogios, 38, and Tony Golossian, 61, were arrested at their homes Saturday Strike Force Wanda, but after being taken to Burwood police station, Golossian was then taken to hospital after complaining of chest pains.
Psichogios and Golossian portrayed themselves as members of the Greek Orthodox and Coptic Orthodox communities, police say.
They are said to have committed the offences over a period of four years on a woman who believed she was cursed.
Police allege the older man claimed to be a spiritual mentor who was able to speak to angels, remove curses and banish evil spirits.
They also say the victim believed she and her family had been cursed by a member of the Greek community practising black magic and that they would all suffer terrible consequences, including death and illness, unless the curse were removed, Sydney Morning Herald reports.
The woman told police she attended many prayer sessions at various hotels between 2001 and 2005 where she was blindfolded and sexually assaulted.
It is alleged she paid the men between $500 and $1000 for each prayer session and by 2005 had paid at least $70,000.
The two men were both arrested in June - along with Psichogios' 36-year-old wife - over previous allegations of sexual assault on a 40-year-old woman.
Psichogios was charged with attempted sexual assault.
Golossian was charged with three counts of aggravated sexual assault against the woman in Summer Hill and demanding $50,000 with menace.
They were released on bail and subsequently re-arrested and charged with 220 counts in relation to another woman, now aged 30.
At a press conference at Burwood police station acting Fairfield Commander, Gary Bailey, said, "I have never seen anything as bizarre as this or as callous as this before, it's perpetrated on young women in the community who really don't deserve it.''
Superintendent Bailey also said police will allege similar acts were committed against both women.
"Police will allege also that both victims may have been drugged during these incidents.''
He would not discuss the specifics of the alleged acts, how or with what they were drugged.
Superintendent Bailey said police could not rule out the possibility there had been other victims.
"Two extremely courageous women have already come forward with information which has led to the arrests of these two men," Supt Bailey said.
"We will allege these women have been the cruel prey of callous individuals who used religious fear to manipulate and abuse them for their sexual gratification and financial gain.
"Sexual offences are heinous but an offender who hides behind the cloak of religious respectability is particularly vile,'' Superintendent Bailey said.
"Our investigations are far from over and we cannot rule out the possibility of other victims and I would urge any woman or person, particularly in the Greek Orthodox or Coptic community, with any information to come forward.
"These two women have already shown tremendous strength and courage to overcome the embarrassment and shame they feel to contact police.
"For that they deserve to be acknowledged.''
Golossian, in hospital now and under guard, will be charged with 151 offences when he is released. He may also face bedside hearing. His partner in crime is already behind bars, with 78 charges to his credit.