Gylfi Sigurdsson broke the deadlock for Spurs in a first half controlled by Spurs, but Chelsea responded strongly and equalised thanks to a John Terry header midway through the second period.
Fernando Torres was controversially sent off with nine minutes remaining but Tottenham could not find a winner in the closing stages.
Torres was given the nod up front for Chelsea but Juan Mata again had to settle for a place on the bench as Mourinho opted to reinforce his central midfield, and there were few gaps for either side to exploit in a tight early period.
It was going to something clever to carve out an opportunity and Spurs crafted a delightful move to open the scoring in the 19th minute as Roberto Soldado laid the ball off to Sigurdsson following good work by Christian Eriksen and the Icelandic player burst through a weak Terry challenge before calmly slotting past Petr Cech and into the bottom corner.
All the pre-match talk had been about Villas-Boas' relationship with his former mentor Mourinho and the home crowd took great pleasure in taunting the Chelsea boss, singing: "You're not special anymore."
The hosts almost doubled their lead a couple of minutes later when Andros Townsend beat two defenders with a smart piece of footwork and allowed Soldado to deliver an inviting low cross towards Paulinho in the centre, only for Branislav Ivanovic to make an excellent last-ditch clearance on the edge of the six-yard box.
Tottenham continued to look dangerous in possession as Eriksen produced some exquisite touches, but Chelsea gradually forced their way back into the game and enjoyed a decent spell of pressure before the interval.
They were limited to a series of half-chances due to Spurs' defensive discipline, though, as Eden Hazard had a shot deflected wide and Oscar's well-controlled volley from 20 yards was hit straight at Hugo Lloris, while Terry headed powerfully over.
A stunning counter-attack nearly resulted in a second goal for Tottenham just before the break as Kyle Walker's back-heel released Townsend to sprint clear down the right and he picked out Paulinho with a fine pass, but the Brazilian's strike from a narrow angle ricocheted off the outside of the post.
Mata replaced John Obi Mikel for the start of the second half and Chelsea were almost level within three minutes as Torres skipped away from his man and sent in a cross from the right which a stretching Oscar was just unable to turn home at the far post.
Torres remained at the centre of the action as he was booked after raising his hands to Jan Vertonghen, with replays suggesting he had scratched the Belgian's face.
Moments later Torres raced past Michael Dawson before drawing a fine save from the onrushing Lloris.
A Mata goal was correctly ruled out for offside and Lloris denied Hazard, but Chelsea's dominance was finally rewarded in the 65th minute when Mata floated in a sumptuous free-kick from deep and Terry's glancing header found the bottom corner.
Chelsea kept up the intensity and could have gone in front when substitute Andre Schurrle was played in by a beautiful pass from Torres, but Lloris charged off his line to make a wonderful save.
Torres was dismissed in the 81st minute after being given a second yellow card following an innocuous-looking aerial challenge with Vertonghen, leaving Spurs with a numerical advantage for the final stages.
Jermain Defoe, on for Soldado, spurned a glorious opening as his shot was well held by Cech, while Sigurdsson hit a volley agonisingly wide from outside the area in a frantic finale as a thrilling derby ended with honours even.