Makarova dropped her serve three times and was comprehensively outplayed in the first set against Williams, the second-oldest player in the tournament at 33.
The seven-time Grand Slam singles champion also had chances in the second set, missing a break-point opportunity to go up 4-2, but then serving three consecutive double-faults after leading the ninth game 40-30 to surrender a break, reports Xinhua.
The 33-year-old Williams came back strongly in the third set to take a 3-0 lead but Makarova rallied again and took advantage of Williams' 21 unforced errors to win the deciding set 6-4.
"I have to give her (Makarova) a lot of credit," said Williams. "She was really determined and just kept playing hard."
"I have had issues for the last 12 months, but this year I definitely am looking forward to having a good run and feeling well."
It was only the second time in her 14 appearances that Williams lost in the first round at the Australian Open, where her best result was a runner-up in 2003. She lost to her sister Serena in that final.
Makarova will meet Irina Falconi of the United States in the second round.
--IANS (Posted on 13-01-2014)