The news of Middleton making his first All-Star appearance comes a week after he finished 11th among Eastern Conference frontcourt players to determine this year's All-Star starters.
Both Wade and Nowitzki are expected to retire after this season.
The starting lineups are decided through a voting process in which the players, media and fans all vote for five players from each conference.
James and fellow captain Giannis Antetokounmpo will choose their teams on February 7.
Of course, plenty of talented players have earned their selection this season. Team LeBron will make the first pick in the first and third rounds and Team Giannis will have the first pick in the second round.
Ahead of his 14th All-Star selection, Nowitzki ranks seventh on the National Basketball Association all-time points list (31,275) and is the career scoring leader among worldwide players.
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"And I think I appreciate it more getting in this way".
This is D-Wade's farewell season, and being part of the All-Star game for one last time is something that he rightfully deserves. As of Thursday night, Russell Westbrook is officially a Western Conference reserve - the eighth career All-Star nod for the Thunder's superstar point guard. The game will be broadcast on TNT.
The two have twice faced off in the NBA Finals, with Wade's Heat winning in 2006 and Nowitzki's Mavs claiming the title in 2011. He is a three-time champion and one-time Finals MVP.
"I'm glad I can share this opportunity with Dirk, one of the game's greatest players, someone that I've had battles against", Wade said. And James has the top pick in the third round, which will be the one that includes Wade - his former teammate, close friend and fellow 2003 draft alum - and Nowitzki.
When it was posed to him that James has dibs on the "Special Roster Additions", Wade cheekily retorted: "He better pick me, I'm not even gonna play around".