Title favourites Carlos Moya and Ivan Ljubicic scored contrasting wins to book berths in the semi-finals of the Chennai Open on Friday.
Also progressing to the last four was second seed Radek Stepanek, who has been overshadowed by the stars in Chennai, and Kristof Vliegen.
Defending champion Moya overpowered Germany's Bjorn Phau in the third set to win 6-4, 4-6, 6-1.
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Muller probably thought he was still playing Rohan Bopanna. His strategy of slicing the ball, which had worked well against Bopanna in the second round, played into Ljubicic's hands.
He failed to raise his level to counter the top seed and was plagued with too many unforced errors. The 22-year-old seemed nervous facing the world number nine and his serve caved in during the first set, getting only 48 percent of the first serves in.
Ljubicic broke him in the fourth game of the first set, when Muller served three double-faults.
After fighting hard for his first service game in the second set and holding it to 3-3, Muller finally cracked in the seventh game. The two errors on the forehand on the last two points, after he was leading 40-15 in the ninth game, summarised his game on Friday.
The Croat may not have an attractive one, but the solidity and temperament on court showed why he has risen to the top ten.
"It was a much easier game than I expected," said Ljubicic. "He missed a couple of balls in the beginning which he shouldn't have and basically never came back after that."
Ljubicic plays his next match against Kristof Vliegen, who knocked out four-time finalist Paradorn Srichaphan in straight sets earlier on Friday.
"He (Vliegen) played an amazing game today. I watched the entire match on TV. He looks on fire this week and will definitely try hard after getting to this stage. He doesn't have anything to lose," Ljubicic summed up his next opponent.
In the bottom half of the draw, it will be the battle between the second and third seed. Phau gave Moya a difficult time, but the Spaniard's experience and power saw him through. After hitting some amazing passing shots in the first two sets, the German finally ran out of gas in the third.
Defending champion Moya also stepped up his game and started attacking the Phau serve, which is not one of the best on tour. The seventh seed's average first serve speed was 180 kmph and Moya anticipated it to perfection, pulling in some stunning returns down the line.
The 29-year-old also used his experience hand to move Phau from side to side and tire his legs out. He went into the lead by breaking Phau in the first game of the third set and commanded the game from thereon.
"He was very fast on the court but I am happy to score a good win here," said Moya.
As always, the crowd was behind the two-time champion, and Moya thought they motivated him through the deciding set.
Stepanek, who has had the best run amongst the seeds, had another easy day in the office, beating Thierry Ascione of France 6-3, 6-4.
Results: K Vliegen bt P Srichaphan 6-1, 6-2; R Stepanek bt T Ascione 6-3, 6-4; C Moya 6-4, 4-6, 6-1; I Ljubicic bt B Phau 6-1, 6-3; L Dlouhy/P Vizner bt R Schuettler/ A Waske 6-4, 6-4; P Amritraj/R Bopanna bt P Srichaphan/R Stepanek (retd).