With the players engaging in hard-hitting baseline rallies, it was Halep that came out on top, breaking serve with a backhand crosscourt to lead 5-4 and then sealing the match with a trademark forehand to complete victory in 77 minutes.
With Svitolina losing in the quarterfinals to Caroline Garcia, Halep needed to reach the final in order to get past Muguruza.
But the Romanian is in red-hot form and claimed the scalp of former world No. 1 Maria Sharapova earlier this week, beating the Russian at the eighth attempt.
Halep was always in control against the world number eight Ostapenko and put herself on the path to victory when she broke the Latvian in the first game of the first set.
"It was a great match, I think I played my best tennis against her", Halep said.
In contrast, Zverev smashed his racquet on the floor, earning a warning from the umpire, when Kyrgios grabbed the decisive break in the second set. "I really want to do better, and I know I have to try to dominate the point or I will run a lot".
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The last Premier Mandatory event of the season has turned into a place of retribution Halep who cast out some of her recent demons.
That said, with 9 of the Top 10 players entered (only Venus didn't make the trip), Simona Halep was the only Top 8 player to make the semifinals. She defeats the French Open champion to advance in Beijing, winning in straight sets.
In addition to doubling her winners (12) to unforced errors (6), the Romanian also served very well, which was unquestionably an area that Sharapova had been able to exploit in their seven prior meetings. At Roland Garros, she lost to Ostapenko in the final to be denied the opportunity to climb atop.
The 26-year-old will take over top spot from Spain's Garbine Muguruza and she admitted it was a day she would never forget.