The tussle between the defending champion and the old master failed to live up to its billing.
The 33-year-old Spaniard, who won the tournament four times in a row between 1993 and 1996, was out of her depth against the Frenchwoman who stayed on course for her fifth final in six years in the Italian capital.
Martinez lacked power and precision on her groundstrokes and made a string of mistakes to effectively gift the match to her opponent.
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Four games later a double-fault and a backhand that looped over the baseline gave Mauresmo another break point, which she converted with a crosscourt pass to effectively close out the first set.
Another spate of unforced errors by Martinez led to her losing serve to love twice at the start of the second set, as Mauresmo established a 3-0 lead before closing out the match in less than an hour.
She next faces the winner of the match between sixth seed Vera Zvonareva and in-form Italian Francesca Schiavone.
Later on Friday, top seed Maria Sharapova takes on fellow Russian Elena Bovina.
