In doubles, Martínez Sánchez won 21 WTA Tour titles, ten partnering with her compatriot Nuria Llagostera Vives.

She made her first Grand Slam draw at the 2001 Australian Open losing to the third seed Venus Williams, in three sets.

She defeated Anastasiya Yakimova, Arantxa Parra Santonja and Betina Jozami to reach the semifinals where she won a close two-setter against Patricia Mayr.

Williams insisted that the ball had hit Martínez Sánchez's arm, not her racquet (which replays confirmed), but the umpire refused to change the decision.

Williams, annoyed, threatened Martínez Sánchez, stating, "I'm gonna get you in the locker room girl, you don't know me."

As the third seeds, they defeated Venus and Serena Williams, before winning the biggest title of their careers against world-number-ones, Cara Black and Liezel Huber, in the final.

In doubles, she won seven titles with Llagostera Vives, at Bogotá, Acapulco, Barcelona, Palermo, Toronto, New Haven, and the most important, the WTA Tour Championships in Doha.

They reached the Final after defeating top seeds Australia, the United States, and Romania without losing a single match.

Martínez Sánchez major breakthrough tournament came at the Italian Open, a Premier 5 event in Rome where nine of the top ten women were competing.

This time would be worse for she would miss Wimbledon and most of the summer season, before returning in New Haven and losing in the first round against wildcard Elena Dementieva.

In the US Open, she failed to repeat her third-round finish of the previous year, losing in the second round against Patty Schnyder in a tight match.

Overall, the result was good for Martínez Sánchez who had made a lot unforced errors, and Schnyder who had her best match in the past few months.

Martínez Sánchez experienced even more success in doubles where she reached the semifinals with Llagostera Vives, losing to eventual champions and No.

Martínez Sánchez lost to Laura Robson and Ana Ivanovic both in three sets, at the Eastbourne International and Wimbledon, respectively, the first sending her out of the top 50.

However, in doubles, again with Llagostera Vives, they won in Eastbourne without dropping a set and defeating the top-2 seeds, but they lost in the quarterfinals of Wimbledon to Flavia Pennetta and Francesca Schiavone in a tough three-setter.

She and Llagostera Vives routed Casey Dellacqua and Sam Stosur (6–1, 6–1), before falling to Peng Shuai and Zheng Jie (4–6, 2–6).

After a tough first-round match with fellow veteran Mirjana Lučić winning 6–3, 7–5, she pushed eventual champ Serena Williams, 6–2, 6–4.

After a series of tough wins with Llagostera Vives in doubles, they met the eventual champions Sara Errani and Roberta Vinci, falling 2–6, 3–6.

[4] Entering the Korea Open as the defending champion, she played well defeating Eleni Daniilidou,[5] and Nadia Petrova via walkover, but lost in the quarterfinals where she was routed by Ekaterina Makarova 1–6, 1–6.

[7] After giving birth in November 2013 to a daughter, Andrea,[8] she returned on the main tour in the Miami Open doubles draw, pairing with Vera Dushevina.