"I knew how to play Roddick as I beat him last year," Monfils said. "I am tall and can reach a lot of his serves."
Monfils had eight aces and was successful with strong forehands and drop shots from the baseline.
The second-seeded Roddick was broken for the first time in the tournament while serving for the first set at 5-4. Another break by the 75th-ranked Monfils won him the first set.
Roddick missed three break points in the first game of the second set, and suffered another break immediately afterward. He then got warned for smashing his racket to the court.
Roddick missed two more chances on Monfils' service at 4-1 down.
"I was actually hitting the ball better than in my previous matches here," Roddick said. "Normally you win the point when you hit the ball in a corner three times -- but not so against Monfils. He's a great athlete and seems to get every ball back."
Hewitt broke Hartfield two times to build a 3-0 lead in the first set.
"It was very important for me to start well and put him under immediate pressure," Hewitt said.
Hartfield broke back once, but got hardly any chances in the service games of Hewitt, who ended the match with an ace on his first match point.
Top seed Amelie Mauresmo overcame her French compatriot Emilie Loit 7-6 (7/3), 6-3 to seal a place in the semi-finals of the WTA tournament on Thursday.
Mauresmo, who is using this event on clay to prepare for the French Open, was set to face the winner of Thursday night's quarter-final between France's Marion Bartoli and Russia's Elena Vesnina.
Mauresmo said afterwards: "I had a real battle today. It was a close match, I started well but then I let things go a bit although I played better than yesterday. I'll need to get better towards the end of this week."
The winner of the Australian Open and Wimbledon last year Mauresmo is appearing here after suffering a second round shock to Australia's Samantha Stosur last week.
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