World number seven Sabalenka squandered a one-set lead to lose to Barty in the Stuttgart Open final two weeks ago.
But she will have another crack at winning silverware in the Spanish capital in Saturday's final against Barty, who saw off Paula Badosa in straight sets in the other last-four match.
"I'm looking forward to the final," she said in her on-court interview. "First of all I will have a good rest and do everything I can to prepare myself as good as I can.
"It'll be really interesting to play another final against Ash. I think it'll be a great battle. I think everyone coming here can see themselves winning the tournament. I'll do my best."
Sabalenka had not dropped a single set in Madrid in the lead-up to the semi-final and that remains the case after cruising past Pavlyuchenkova in a little over an hour.
The fifth seed converted four of her five break points and won 73 per cent of her second-service points.
Pavlyuchenkova, ranked 41st in the world, lost serve in the fourth and eighth games of the opening set and failed to hold on her first two service games in the second set.
Despite breaking Sabalenka in the seventh game, the Belarussian proved far too strong for her opponent and got over the line with a fourth ace of the match to reach her third final of the season.
Sabalenka wrapped up the first set to love in just 25 minutes as an unusually sluggish Barty struggled to find any kind of rhythm to her game.
Barty, who had won 16 consecutive matches on red clay, rallied in the second set to get herself back on level terms.
At 4-4 in the deciding set Sabalenka broke Barty and then held her nerve on serve to secure her 10th WTA Tour career title which will see her climb up to fourth from seventh in the world rankings on Monday.
Barty was on a streak of nine consecutive WTA Tour titles and had not lost to an opponent in the top 10 since the WTA Finals in 2019.
But in-form Sabalenka had not dropped a single set in Madrid in the lead-up to the final and began in imperious fashion.
The 23-year-old from Belarus produced a clinical first set, dropping just four points, as Barty failed to win a single game in the set to record a bagel for the first time in four years.
The pair exchanged breaks in the second set before Australian Barty, 25, finally discovered some momentum to break her opponent again to seal the set.
Sabalenka squandered a one-set lead to lose to Barty in the Stuttgart Open final two weeks ago.
And Barty, also playing in the final of the tournament for the first time, had threatened to break her opponent at 4-3 in the decider.
But this time Sabalenka took her chance when Barty fluffed a drop shot and then double faulted to give her three break points, converting at the first time of asking with a powerful backhand.
Sabalenka then clinically sealed victory with a flawless service game to love, clinching victory when Barty smashed a forehand into the net.
"To be honest, after the final in Stuttgart I was injured, I couldn't move and wanted to withdraw," Sabalenka said in an on-court interview after the win.
"But the recovery was good, in four days I feel better and now I'm the champion. It's been an amazing week."
Teichmann produced an astonishing fightback to beat fourth seed Svitolina 2-6 6-4 7-6 (7-5) at the Caja Magica.
Unseeded Swiss Teichmann came from a set and a break down to claim the scalp of the world number five, who squandered a commanding 5-1 lead in the final set.
Svitolina saw six match points come and go in an incredible deciding set, opportunities she was left to rue when the 40-ranked Teichmann won a tie-break to end a contest that took two hours and 33 minutes to settle.
World number one Barty extended her winning run on clay to 12 matches with a 6-2 6-1 success over Shelby Rogers.
Barty claimed her third title of the year in Stuttgart last weekend and the Australian needed just an hour to send Rogers packing, losing just two points on her first serve and not facing a single break point.
French Open champion Iga Swiatek was also an emphatic winner, easing past another American in the form of Alison Riske 6-1 6-1.
Swiatek, making her debut in this tournament, has won 16 consecutive matches on clay after blowing Riske away.
Defending champion Kiki Bertens beat 15-year-old Victoria Jimenez Kasintseva 6-4 6-0, while Petra Kvitova progressed when opponent Marie Bouzkova retired due to hand injury after the Czech won the first set.
Garbine Muguruza was forced to withdraw ahead of her meeting with Sloane Stephens due to a leg injury. Belinda Bencic, Angelique Kerber and Johanna Konta were among the other winners in the Spanish capital.
The world number 11, who was a shock winner at Flushing Meadows last September, announced on Tuesday she and Torben Beltz would no longer be working together.
German coach Beltz came on board in November but departs as Raducanu plots the way forward ahead of the French Open and Wimbledon. The 19-year-old Raducanu says she needs "a new training model".
Beltz becomes the third coach to move on from working with Raducanu in the last 12 months. She swapped Nigel Sears for Andrew Richardson, who was in her corner at the US Open, before electing to bring on board the experienced Beltz, who previously worked with Angelique Kerber and Donna Vekic.
Raducanu said of her decision: "I want to thank Torben for his dedication. He has a huge heart and I have enjoyed our strong chemistry during the time together."
She is preparing to play at the Madrid Open and will be assisted there by Iain Bates, the long-serving head of women's tennis at the Lawn Tennis Association (LTA).
Raducanu has yet to indicate what direction she will go in regarding her next full-time hire, although working with the teenager is likely to remain an attractive prospect for leading coaches.
She said: "The best direction for my development is to transition to a new training model with the LTA supporting in the interim."
Although Raducanu has continued to climb the WTA rankings, she has managed just five wins from 12 matches on tour this year, losing a close contest to world number one Iga Swiatek in the Stuttgart quarter-finals last week.
