In a warm-up ahead of this month's Australian Open, Sharapova converted 75 per cent of her break points, against just 13 per cent by Williams.
Both players appeared in trouble in the baking heat and low sun at his beachside resort, with Williams particularly struggling to keep the ball on the court.
Story continues below ↓advertisement | your ad hereSharapova, the world No. 14, displayed a solid and fierce baseline game to put Williams away in just one hour and 34 minutes, and record her first win over the American since 2007.
Sharapova broke Williams three times to take the first set which was over in 49 minutes. The second set was on serve until the final game when Williams missed two forehands to lose the match.
"It's good to be back. I'm glad to play against Venus in my first match of the year," said the 22-year-old Russian.
"I still remember when I first came here (in 2005). I was still young and had a great match with Venus."
Williams, who will still be chasing her first Australian Open title when she goes to Melbourne, acknowledged she was a little off the pace after the offseason.
"Maria played so well," Williams said. "I was slow in my first match of the season. It's good to be here hitting the ball."
Sharapova won the Australian Open in 2008, but was not able to defend her title last year due to a shoulder injury.
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