The sixth-seeded Russian player took advantage of Pin's disjointed service game for six breaks while also defending seven of eight break chances on the outdoor clay.
Two seeded players failed to reach the second round on Tuesday with Kaia Kanepi and Sorana Cirstea both exiting.
Lucky loser Masa Zec Peskiric of Slovenia overcame 12 double-faults and rallied for a 3-6, 6-2, 6-4 victory over the fourth-seeded Kanepi, while Belorussian qualifier Anastasiya Yakimova scored a 7-6 (2), 7-6 (5) win over the eighth-seeded Cirstea.
Zec Peskiric had replaced third-seeded Anabel Medina Garrigues after the Spaniard pulled out with an abdominal strain.
Nicole Vaidisova won 82 percent of her first service points, including seven aces, to beat Ukrainian qualifier Yevgenia Savranska 6-2, 6-4. The Czech player will next face Francesca Schiavone after the Italian beat Lourdes Dominguez Lino 7-6 (4), 6-4.
Fifth-seeded Carla Suarez Navarro needed just under an hour to dispatch fellow Spanish player Estrella Cabeza Candela 6-2, 6-0. Suarez Navarro will face Emilie Loit of France, who beat Mervana Jugic-Salkic 7-6 (3), 3-6, 6-2.
In the rest of Tuesday's first round matches, Severine Bremond of France beat Anna-Lena Groenefeld 7-6 (4), 6-2 and Germany's Tatjana Malek was a 6-3, 3-6, 6-1 victor over Nuria Llagostera Vives.
On Monday, top-seeded Alize Cornet of France was upset by compatriot Stephanie Cohen-Aloro.
Top-seed Cornet ousted at Barcelona
