According to Djokovic, Pospisil served ‘extremely well’ in the second set, which put added pressure on his game.
"That's why the second set was very close," added Djokovic following his 6-3, 7-5 victory.
"He had a set point on his serve. But I fought my way through. I believed I could recover from break down, and I did. I think it was a very high-quality tennis match."
Djokovic is bidding for his fifth title in Beijing, a tournament he has won every year since 2009 apart from 2011 when he did not take part.
In the women's competition, fourth seed Sharapova got off to a flying start in her match, racing to a 5-0 lead over Carla Suarez Navarro.
The Spaniard was a match for the world number four in the second set, but Sharapova was dominant at the tie-break, finishing the match 6-1, 7-6 (7/3).
Meanwhile, world number three Kvitova opened her campaign to win a second consecutive event in China in commanding style.
The Czech player defeated home-crowd favourite Peng Shuai 6-4, 6-2 in her first match since her victory at the Wuhan Open last Saturday, advancing in Beijing with the same confidence she showed at the earlier tournament.
World number eight Caroline Wozniacki was hoping to confirm her place at the tournament with a deep run in Beijing, but crashed out in her first match 6-4, 7-6 (11/9) at the hands of Samantha Stosur.
Alize Cornet of France eased past American Lauren Davis 6-2, 6-1 in the day's only other women's match in Beijing, where much of the programme was affected by rain.
Nishikori fires to victory
Kei Nishikori thrilled his home fans as the US Open finalist posted a 6-3, 6-4 opening victory over Ivan Dodig yesterday to reach the second round of the Japan Open.
The fourth-seeded Nishikori could do no wrong at the Ariake Colosseum, where the roof was closed due to intermittent rain after two days of sunshine in the capital.
Nishikori, last week's champion in Kuala Lumpur, next faces Donald Young after beating the American in both of their previous ATP matches.
"Winning Kuala Lumpur gave me more confidence,” said the Japanese sporting idol. “I try not to pay attention to the crowd or what the opponent is doing, but it's always good to play at home.”
Japan's top player is working to become the first Asian man to qualify for the eight-strong field at London's World Tour finals in November.
Nishikori currently stands provisional sixth with five spots in the field still to be filled over the next month of regular-season ATP play.
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