Michele Elliot of UK-based child protection charity Kidscape told Al Jazeera: "Usually when you break up these rings you don't end up identifying the children or taking them away from the situation, so that is one of the things that has delighted us."
"There are thousands and thousands of perverted people out there who get pleasure out of watching children getting sexually abused and it is just a horrendous industry," she added.
The investigation involves agencies from 35 countries and has gone on for 10 months.
Authorities said the host of the website, Timothy David Martyn Cox, 27, of Buxhall, who used the online identity "Son of God", admitted nine counts of possessing and distributing indecent images.
Forensic teams found 75,960 indecent and explicit images on his computer, in addition to evidence that he had supplied 11,491 images to other site users.
After his arrest, British, Canadian and Australian authorities were able to infiltrate the chat room and collect evidence on the other members.
Officers posed as contributors and even pretended to be Cox, running the chat room for 10 days. At no point did officers distribute illegal images, authorities said.
Authorities said they used surveillance tactics normally used against terrorism suspects and drug traffickers to infiltrate the paedophile ring.
Officials did not provide a full breakdown of which countries were involved, but identified Canada, Australia and the United States as British officers' main partners in the investigation.
Toronto police conducted online surveillance along with British police, Detective Sgt Kim Scanlan of the city's police sex crimes unit said.
She said 24 Canadians had been arrested and seven Canadian children rescued since late 2005. "Every arrest we make we seize computers and information so there are a number of ongoing investigations," Scanlan said. "There's just been great cooperation. It's a good day, but it's one day out of many."