Reigning champions the Spurs - missing Tim Duncan, Tony Parker, Manu Ginobili and Daniel Green - were no match for the Mavs, who ran out 99-93 winners in Dallas.
The match-up saw four-time NBA MVP Rondo make his much-anticipated debut for the Mavs (20-8) following his departure from the Boston Celtics on Thursday.
Rondo was three of 11 from the field for six points, nine assists and seven rebounds at the American Airlines Center.
"It was exciting. The best part about it was we got the win tonight. It was a tough grind game, but we stuck with it and got the win," said the 28-year-old.
"I just try to do the intangibles. I didn't make a lot of shots tonight, so I just wanted to go in on the defensive end of the floor and make plays for my team and get the ball back for more possessions."
While all the hype surrounded Rondo, the game belonged to team-mate Monta Ellis.
Ellis posted a game-high 38 points, with 11 of those scored in the final four minutes.
"He scored 38 points, so I didn't hold him back too much," said Rondo. "We both like to dominate the ball, but I think we played well off each other tonight."