By Peter Simpson
"It feels good to be back at a court where I've had a lot success in the last couple years," said the 2008 Beijing Olympics bronze medalist.
Djokovic enjoys a 4-3 winning record over Murray although he was beaten the last time the pair met 18 months ago in Miami.
Murray appeared to have shrugged off the jetlag that kept him awake for hours following his arrival in Beijing and demolished the error-prone Frenchman, firing 10 aces during the lopsided encounter.
"I served quite well today. I didn't once get broken and served a lot of aces," said the Scot before adding he was felling better after a week of illness.
"I started the match well and didn't give him any opportunities except in the second set at 3-2. I think that was the only game where he had a couple of break points on my serve. It was a good first round."
The 23-year-old added to Mathieu's frustration by breaking his serve four times in front of small but noisy partisan Chinese crowd sporting several Scottish flags.
Even a hatful of reckless backhands by Australian Open finalist failed to flatten the 107th ranked Frenchman, whose flashes of brilliance rarely tested Murray.
Former world number one Maria Sharapova and Chinese crowd darling Li Na are also seeking to progress in the women's tournament which is running alongside the men's competition.
(Editing by Pritha Sarkar)