The Celebrity Big Brother star is fronting 10-hour 'presenting' slots with Studio66tv one day a week where she is available for one-to-one calls.
The satellite station – based at studios in West London – encourages callers to call premium-rate phone lines to speak to glamour models.
The 21-year-old from Coulsdon, Surrey, has now been dumped by her agent after it was revealed she works for the channel.
Some models strip and engage in sex talk but it is understood Ayling signed up for daytime shows between 12pm-10pm – where chats are not of an adult nature and she will not take part in private webcam shows.
Her first show took place on Monday.
A spokesman for the station said: "Having worked with Chloe on Sixty6 Magazine we know what a great girl she is.
"We are super excited to have her now join us on Studio 66 and give her fans the chance to speak to her and get to know her better.”
Ayling hit the headlines last year after being abducted in Italy and offered for sale as a sex slave on the dark web.
Lukasz Herba, 30, was jailed for 16 years in June for her abduction.
Chloe has always denied suggestions the kidnap was a publicity stunt.
She has since released a book about her ordeal and appeared on Celebrity Big Brother.
The reality TV star's agent Alistair Sington, of Kruger Cowne, told Mail Online the agency has severed ties with Ayling after her new line of work emerged.
He said: "Kruger Cowne started working with Chloe after she returned from her horrendous kidnapping ordeal in Milan. We helped to steer her through the subsequent months of media criticism and disbelief which finally ended when her story was found to be true by the court in Milan which sentenced her kidnapper to 16 years in prison.
"Our agreement with Chloe has always been on the understanding that we could only represent her so long as she didn't return to a career as a paid glamour model.
"Chloe has decided she now feels comfortable returning to that career, and as a result we have decided that we can no longer represent her.
"I have spoken to her to inform her of our decision and we wish her well for her future career."
The firm represents a host of stars including presenter Adrian Chiles and comedian Lenny Henry.
The Sun has previously reported how Chloe's kidnapping will be turned into a movie.
Chloe Ayling has been contacted for comment.
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