Muguruza, who was a late entry to the event after U.S. Open finalist Karolina Pliskova pulled out, will next play Monica Niculescu of Romania.
A sublime disguised lob set up break point and when Djokovic fired wide to hand over the set, he snapped and repeatedly slammed his racquet into the deck.
The Spaniard's through to his first Masters final, while Djokovic concedes he's struggling with the mental side of the game.
Then Djokovic, angry at failing to secure a break point in game five, petulantly tore his shirt at the neck and went to change it mid-game, receiving a time violation warning.
Both men exchanged breaks during the second set and Djokovic allowed Zverev to trim his lead to 5-4 in the tie-break, leaving him perilously close to defeat, before he eventually levelled the match.
Djokovic then showed why he is now the world's best player.
Roberto Bautista Agut made a disgruntled Novak Djokovic pay for another lacklustre display by claiming a stunning victory over the world number one to reach the final of the Shanghai Masters. "I think putting a lot of rhythm to make the match with high intensity was the key to beating him".
Conte says Kante was great buy for Chelsea
The Italian has compared Vardy to a radio because of the incessant noise he makes and he wants them all on the same frequency. Good game from the start, I asked that we start well with intensity, to try to do what we're doing during training sessions .
No. 1 Alabama trounces No. 9 Tennessee in 49-10 runaway
O'Brien sustained a head injury in the loss to Texas A&M, and he subsequently was dismissed from the team for a rules violation. Alabama has been able to play tight defense and is averaging over 44 points per game, making it very hard to compete with them.
Djokovic smashes his racket after hitting a backhand wide to lose his serve in the second set.
Djokovic's cautious welcome contrasts with the reaction from Rafael Nadal, who said tennis thrived on long and "dramatic matches that become emotional".
In the first set against Zverev, things couldn't have gone much worse. He was fighting, he was focused. I was quite flat with my feet. "I played solid at the end of the second and third sets".
He'll face the victor of the second semifinal between second-seeded Andy Murray and Gilles Simon.
Djokovic lost for the seventh time this season.
Murray, the world number two, and Gilles Simon play later to decide who will meet Bautista in Sunday's final.
In the women's WTA Hong Kong Open, fifth seeded Caroline Wozniacki booked her place in the summit clash with a 6-3, 6-4 victory over defending champion and seventh seed Jelena Jankovic. "I was using it to just forget about my mistake, and it worked I hope".