Her sister, Venus, who lost to Serena in the 2017 final, opens her tournament against Belinda Bencic of Switzerland.
While there are many major sporting events that grace the stadiums and streets of the Victorian capital of Melbourne, Australia, none have a bigger impact on the city than the Australian Open.
Australian bad boy Bernard Tomic was fined a third of his Â£35,000 ($47,500) prize money for unsportsmanlike conduct at Wimbledon, after saying he felt "bored" and "couldn't care less" following a straight-sets defeat on day one.
That means they can only play each other if they set up a rematch of last year's final.
It was a welcome sight for Australian Open organisers and fans following the withdrawals of five-time runner-up Andy Murray and Kei Nishikori as well as 23-time slam victor Serena Williams on the women's side, but Djokovic insisted he is still not 100 per cent fit with the tournament set to get underway on Monday.
The six-time Open champion played his first exhibition matches in six months on Wednesday, and reported delight at his performance - and no pain from the hit-out.
Bookmakers are tipping the world No. 2 and tournament's second seed to win the title at A$2.75 (S$2.88).More news: Rain expected Tuesday, Thursday and Friday
"I knew that I can not make it with only Futures so I had to step up my game and try to compete at a higher level", explains Maamoun.
Elsewhere, Agnieszka Radwanska kept her preparations for the year's first Grand Slam on track with a 7-6 (7-4), 6-0 win over teenage American qualifier CiCi Bellis.
"Luckily for me, I'm here", Djokovic said after he beat Thiem on Wednesday.
Federer also has Milos Raonic, Juan Martin del Potro, David Goffin and Tomas Berdych in his quarter of the draw, while Nadal would appear to have the easier section, although former U.S. Open champion Marin Cilic looms as a last-eight opponent.
"Mentally, it's not there but, hopefully, I can get there all together by the first round".
Nadal hasn't played competitive tennis since withdrawing from the season-ending ATP World Tour finals due to a knee injury.
There will be many that question the 30-year-old's chances of coming anywhere near to winning a record seventh Australian Open but the very fact he is going to be competing will prove an unwelcome sight for his main rivals. Former world No. 1 Moya will lead the Mallorcan's team, after spending last season with Rafael and Toni preparing for the latter's retirement, having helped Nadal roar back to life after a barren three-year spell without a Grand Slam trophy.
Venus Williams, who lost the Australian final to her younger sister Serena a year ago, is seeded fifth.