On a sweltering evening in the Thai capital, Mourinho watched his senior players get their first proper run-out of the pre-season campaign.
The only goal of the game was scored from the penalty spot by Romelu Lukaku on 34 minutes.
Mourinho's first-half line-up featured new signings Wallace at right-back and Andre Schurrle on the left side of an attacking midfield three.
Both those players impressed in the opening 45 minutes, which included a drinks break midway through due to the humidity at the Rajamangala Stadium.
By that stage, Chelsea had almost taken the lead when All-Stars goalkeeper Kristsana Klanklin collided with his own defender after Ramires had headed Kevin De Bruyne's deep free-kick delivery back across goal. The ball looped onto the crossbar and bounced down, but the hosts eventually cleared.
Wallace won the penalty in the 34th minute, as striker Lazarus Kaimbi came across to intercept the ball in the area but ended up blocking the Brazilian's progress instead. Lukaku sent Klanklin the wrong way from the spot, scoring with a powerful shot low into the left side of the goal.
The introduction of Eden Hazard after the break gave the Chelsea attack some much-needed pep, while new-boy Marco van Ginkel showed discipline in his use of the ball in midfield.
On 66 minutes, the All-Stars had their best chance of the match. A deep pass from a set-piece was floated to the far post where Bukasa Kasonga had escaped his marker, but his poor header did not even trouble goalkeeper Jamal Blackman.
De Bruyne's last act before being substituted on 79 minutes was to send in a fierce dipping free-kick that was well saved. His replacement - 17-year-old Burkina Faso midfielder Bertrand Traore - should have done better with a shot from Gary Cahill's lay-off.
The tempo dropped off in the closing stages and Chelsea ran out comfortable winners. The Blues return to action on Sunday when they take on a Malaysia XI in Kuala Lumpur (kick-off 2.45pm BST).