Jose Mourinho has been without a club since he was ousted as manager of the Red Devils last December, and has taken in roles as a pundit for RT and beIN Sports since then.
Mourinho will be joined in the studio by former Manchester United captain Gary Neville, Jamie Redknapp, Jamie Carragher and Graeme Souness.
The 56-year-old Portuguese won three Premier League titles across two spells at Chelsea, while his two-and-a-half year stay at Old Trafford yielded a Europa League trophy and one League cup.
In a statement released on Saturday morning, Mourinho said: "The Premier League is a special competition for me, one that takes so much hard work to win and you just can't take your eyes off the matches every week.
"Sky Sports is the home of the Premier League and it's a pleasure for me to join this team and help to understand and explain what happened in each match. Football is a huge passion, it means so much to the fans, and I look forward to being part of the Premier League with them until I return to my place on the touchline."
The last time Manchester United and Chelsea met in the opening weekend of the season was in the 2004/2005 campaign when Eidur Gudjohnsen’s solitary goal gave the Blues a slim win at Stamford Bridge with Mourinho in charge of the Londoners for his Premier League debut as a manager.
