The 53-year-old actor, who played Chandler Bing in the classic sitcom, told PEOPLE magazine that he was enamoured with Jennifer Aniston before they began filming in 1994.
“The time I realised I had a crush on Jennifer Aniston was way before the show started.
“It was like two years earlier when I met her and how could you not have a crush on her,” he said of Aniston who played Rachel Green on the show.
“There was such severe indifference from her that I ended my crush, I had to. So, I think I ended it in time.
“But I thank her in the book for allowing me to look at her face for like two extra seconds than normal people would,” he joked.
Further explaining his infatuation he confessed he hid his feelings: “I never said anything, and I hid it, you know, the crush,” he admitted.
“But, you know, then she married Brad Pitt, and I was like ‘I don’t think I have a chance here.'”
In his memoir, ‘Friends, Lovers and the Big Terrible Thing’ which was released earlier this month, Matthew opened up about his battle with addiction and alcoholism.
He recently told ABC News journalist Diane Sawyer that Jennifer Aniston helped him during his struggle.
“She was the one who reached out the most, you know. I’m really grateful to her for that.”
In his interview with PEOPLE, he revealed how he was in the early stages of alcoholism when Friends began.
Over the ensuing years, it got to a point where four years ago, his colon burst from using opioids.
He spent two weeks in a coma and five months in hospital and had to use a colostomy bag for nine months.
"The doctors told my family that I had a 2% chance to live,” he said.
"I was put on a thing called an Ecmo machine, which does all the breathing for your heart and your lungs. And that's called a Hail Mary. No one survives that."
Perry said five people were put on Ecmo machines that night and only he survived, making him question why he was the one.
He said his alcohol addiction began to surface when he was first cast on Friends aged 24.
By the end of the 10th series of the hit show, he became "entrenched in a lot of trouble".
“I didn’t know how to stop. If the police came over to my house and said, ‘If you drink tonight, we’re going to take you to jail,’ I’d start packing. I couldn’t stop because the disease and the addiction is progressive. So it gets worse and worse as you grow older,” he explained.
He has been to rehab 15 times and has had 14 surgeries on his stomach, admitted that fans who read the book will “be surprised at how bad it got at certain times and how close to dying I came”.
“I say in the book that if I did die, it would shock people, but it wouldn’t surprise anybody. And that’s a very scary thing to be living with. So, my hope is that people will relate to it and know that this disease attacks everybody. It doesn’t matter if you’re successful or not successful, the disease doesn’t care.”
“I’m an extremely grateful guy. I’m grateful to be alive, that’s for sure. And that gives me the possibility to do anything,” he continued.
“What I’m most surprised with is my resilience. The way that I can bounce back from all of this torture and awfulness. Wanting to tell the story, even though it’s a little scary to tell all your secrets in a book, I didn’t leave anything out. Everything’s in there.”