"I really gotta stop judging books by their cover," the R&B star, who recently logged studio time with Michael Bolton, tells PEOPLE. "I was expecting him to be really up tight. But he wasn't! He was so relaxed, cool and down to earth."
Ne-Yo, whose album Year of the Gentleman hits stores Tuesday, is getting his character flaw in check – he even issued an apology to pop star Lindsay Lohan in August for doubting her musical abilities.
While Ne-Yo and Bolton spent several hours at a Los Angeles studio, the duo recorded "Call My Name." The song is "about a mistake that a woman has made in choosing between two guys, and he's letting her know 'I'm here regardless; call my name and I'm there,' " Ne-Yo says.
"We sat and talked about all kinds of stuff – how he's newly single, marriage, the road – he was honestly one of the cooler sessions I've been in this year."
Could the song's lyrics have any personal meaning for Bolton, who ended his engagement to Nicollette Sheridan in August?
"Kinda sort of," says Ne-Yo. "But we both agreed that we had been in that boat before."
Many CollaboratorsThese days Bolton is just one of many artists on Ne-Yo's list of collaborators. The in-demand star is still submitting songs for Whitney Houston and Michael Jackson's upcoming albums, too.
"[Michael] will tell me which ones he likes and which ones he doesn't like," says Ne-Yo. "He said, 'Just makes sure it's melodic and something relatable.' He likes a lot of today's music but equally doesn't like a lot of it."
"[Michael] says that if we were to take what Chris [Brown] does with his body and what I do with my voice, then that would be the ultimate Michael Jackson," Ne-Yo says.
Next up for the singer-songwriter? A collaboration with Marilyn Manson.
"I have no idea what it's gonna sound like and I have no idea what I can do for him, but I'm damn excited to figure it out and I know I have the capacity to do it."