Mr Orkopoulos has released a statement saying he's resigned as the endorsed Labor candidate for Swansea.
He was arrested yesterday morning over accusations he sexually abused two teenage boys and supplied them with drugs between 1997 and 2005.
Mr Orkopoulos – who is married with three children -- has been charged with 30 offences including supplying drugs, indecent assault and engaging in child prostitution.
The 49-year-old former Minister for Aboriginal Affairs says he's innocent of all charges, and will vigorously defend his reputation.
He says he and his family have been traumatised by the events, and he's asked the public and the media to respect his right to the presumption of innocence.
Premier 'appalled'
However NSW Premier Morris Iemma wants Orkopoulos out of the state government.
The premier told reporters he found the sex offences and drug charges against Mr Orkopoulos "appalling" and "disgusting".
He also said anyone in the government who ignored prior warnings about Mr Orkopoulos' behaviour would also be sacked from the government.