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World No. 1 Serena Williams, fresh from winning a record sixth Miami Masters title, will seek her third trophy of the season at the WTA Family Circle Cup claycourt event.
Defending champion and top seed Williams, who like the other top-eight seeds received a first-round bye, will play her first match on Tuesday against Italy's Camila Giorgi, who eliminated Mandy Minella 6-4, 6-4 on Monday.
Williams, a 15-time Grand Slam singles champion, won at Charleston in 2008. The 31-year-old American won this year at Brisbane as well as Miami, where she downed World No. 2 Maria Sharapova of Russia in the final.
Danish second seed Caroline Wozniacki has won four clay titles in her career, including at Charleston in 2011.
Wozniacki will open against Spain's Silvia Soler-Espinosa, who outlasted Italy's Francesca Schiavone 3-6, 6-4, 7-6 (8/6) in the opening round.
Australia's third-seeded Samantha Stosur, the 2010 Charleston champion, is also in the mix, playing her first event since pulling out of Indian Wells with a calf injury.
Stosur, of Brisbane, will open against either New Zealand's Marina Erakovic or Slovakian Daniela Hantuchova.
Other seeds in the field of 56 include Americans Sloane Stephens and Venus Williams, Czech Lucie Safarova, Spain's Carla Suarez Navarro and Germany's Mona Barthel.
Puerto Rico's Monica Puig beat Czech Andrea Hlavackova 6-4, 6-0 to book a second-round date with Venus Williams.