Lucie Safarova sparked celebratory scenes after her big hand winner clinched victory as she beat Jelena Jankovic 6-1 6-1.
Petra Kvitova and Safarova had put the defending champions in control on Saturday by winning the opening singles rubbers for a 2-0 lead.
Ana Ivonovic reduced the arrears by beating Kvitova 6-3 7-5 on Sunday.
But Safarova defeated Serb number two Jankovic in one hour and 17 minutes to prevent the first-time finalists becoming the first team in the competition's history to overturn a 2-0 deficit in the final.
The world number 17 hit 32 winners, describing her performance against the world number 22 as one of her best.