The midfielder who was part of United's "Class of 92" also played 66 times for England, retiring after Euro 2004 to focus on his club career.
Scholes is the latest player from Alex Ferguson's United sides to move into management, following in the footsteps of ex-colleagues like Gary Neville, Ryan Giggs and Ole Gunnar Solskjaer.
Scholes, upon his unveiling at Oldham on Monday, was inevitably asked how he'd react to any potential future comments from pundits including Mourinho, who yesterday revealed he'd be returning to football in a new role. I have been quite critical.
"I'm close to Nicky (Butt, United's head of academy) and the people at United, if they can help me I'm sure they will".
If anyone wants to have a pop at me, I won't take any notice.
"It's always been a club fighting relegation as much as other managers have tried to lift it, it's been hard and I'm like every manager who's been here in that time, I want to try and change it".
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There were concerns that his 10% stake in Salford City, the National League club he co-owns, would prevent him from taking charge of the Latics.
Speaking about the appointment, Oldham owner Abdallah Lemsagam said: "Paul has won everything there is to win in football".
"It's no secret how much he has wanted this job in the past and how much he loves this club, so I'm very happy to bring him into our family at Oldham Athletic. There's obviously been three or four times over the last five or six years when it could have happened, but I've not been quite ready, but now I feel, I hope, now is the time and hopefully we can be successful together".
"It's fantastic to have Scholesy back in the game because he was a fantastic player to play with, great personality".