The GM:TV presenter spoke out in an interview on GB News to accuse Schofield of "controlling , coercive behaviour" and claimed ITV had "covered-up" his affair with a young production assistant on the daytime show.
Holmes, 63, said: "It's a total cover-up.
Watch: Eamonnn Holme accuse Phillip Schofield's affairs ITV of covering up
"Those in authority had to know what was going on and they thought they would dodge a bullet with this which they do and they do constantly."
In response to Schofield's latest claims on Instagram that there was "no toxicity" at This Morning he said: "I think that Phillip is absolutely right about toxicity.
"But my friend, the toxicity is not with me, Dan Wootton, or anyone else, the toxicity is with you."
There has long been tension between Holmes and Schofield, 61, so where did it start?
Stand By Your Woman
Back in 2019 it was reported that Holmes' wife Ruth Langsford had made a formal complaint to ITV about Schofield.
Langsford, 63, was said to have been angered when Schofield cut her off during a live link-up form This Morning to Loose Women.
Langsford was telling viewers what was coming up on the show, when Schofield interrupted: "Guys, we're going to have to jump in there and stop you I'm afraid because we're a bit tight for time at this end. Thank you, Ruth."
She retorted: "Well I only had about two more words to say," and looked away from the camera.
Langsford was said to have made a formal complaint to ITV's head of daytime TV Emma Gormley.
Piers Morgan then hinted there was tension between Langsford and Schofield at the NTAs in January 2020.
The TV stars continued to put on a united front at public events, but Holmes has since accused Schofield of being "passive aggressive".
He said: "It's up to Ruth to say how she felt, but I was feeling hurt for her. No one would have snubbed me like that."
When Phillip Schofield came out as gay in February 2020, Holmes was one of the first people to offer him public support on the show, which he and Langsford were hosting that day.
Holmes told him: “Phillip, nobody should be embarrassed about their sexuality.
“It is fantastic that you have spoken out and there will be so many people who will be strengthened by what you said.”
“We’re all here by your side, we’ll be the first to stand beside you.”
But he then went on to joke that he thought Schofield had been about to resign from This Morning and he could have his job.
Pushed off the sofa
Tensions rumbled on for several years, with Holmes and Langsford hosting This Morning on Fridays and the school holidays, when Schofield and Willoughby had time off.
There appeared to be a competitive atmosphere between the two teams, with Holmes and Langsford keen to show that they were just as important as the 'A-Team' presenters.
Then in December 2021 it was revealed that Holmes was leaving the show, because Alison Hammond and Dermot O’Leary were taking over the Friday slot. Langsford stayed on as part of the guest host roster, but Holmes was not happy to get the boot.
Holmes guest hosted the ITV daytime show on and off since 2006, only to be axed after 15 years in 202
He said later: "They're sly. They didn't want to announce that I'd been dropped because it would adversely affect audience figures, so they made it look as if I'd walked away from them rather than the other way round."
The public support for Willoughby and Schofield was dampened in September 2022 over accusations they "jumped the queue" at Queen Elizabeth II's lying in state at London's Westminster Hall.
He said: "They say they didn't get a fast-track – lie. They say they didn't pay their respects to the body – lie. What else were they there for?
"I mean let's just tell the truth about the whole thing, if they messed up, instead of being arrogant and saying, 'oh we were there working as journalists'."
When news broke that Schofield had quit This Morning after 21 years and Willoughby released a statement saying, "The sofa won't be the same without him," Holmes was quick to point out that all was not well between TV's golden couple.
He called Willoughby false and accused her of stabbing Schofield in the back. In his interview on GB News, Holmes also claimed Willoughby's friendship with Hammond wasn't real, and that there was "very little contact" between Hammond and other presenters before.
Schofield has since confessed to having a secret affair for many years with a younger production assistant and quit ITV altogether.
He said in a statement: “Now I no longer work on @thismorning I am free to say this. I hope you have noticed that it’s the same handful of people with a grudge against me or the show who seem to have the loudest voice.
“This Morning is the best show to work on, with the best people. In all the years I worked there there was no toxicity."
But Holmes has pointed the finger back at Schofield.
Watch: Phillip Schofield announced he was stepping down from This Morning 'with immediate effect'