Dinara Safina made her long-awaited return to action and won her first match back, against Agnes Szavay.
Li Na ended a four-match losing streak in the first round then stunned Svetlana Kuznetsova in the second.
Svetlana Kuznetsova, the defending champion in Stuttgart, lost to China's Li Na in the second round.
Caroline Wozniacki, seeded No.1, couldn't find the answers to Lucie Safarova in an opening round loss.
Caroline Wozniacki walked into the sunset after losing her opening match to Lucie Safarova, 64 64.
Yanina Wickmayer, seeded No.8, fell to wildcard Justine Henin in an all-Belgian second round match-up.
Justine Henin let a 63 51 lead slip but would eventually close out compatriot Yanina Wickmayer, 63 75.
Victoria Azarenka met Anna Lapushchenkova in the second round, becoming the Russian's first Top 10 scalp.
Jelena Jankovic made the quarterfinals and fell to Justine Henin in dramatic fashion, 36 76(4) 63.
In perhaps the match of the tournament, Justine Henin outlasted Jelena Jankovic in the quarterfinals.
Jelena Jankovic was as close as ever but fell to Justine Henin again - she is now 0-10 against Henin.
Dinara Safina fell in the quarterfinals to Shahar Peer, her fourth straight loss to the Israeli No.1.
Shahar Peer made the semifinals, beating Dinara Safina along the way, before falling to Justine Henin.
Gisela Dulko and Flavia Pennetta beat Kveta Peschke and Katarina Srebotnik for their fifth title together.
Flavia Pennetta and Gisela Dulko posed with their trophies after winning the doubles final.
Sam Stosur extended her winning streak to 11 matches by beating Anna Lapushchenkova in the semifinals.
Justine Henin and Sam Stosur with their champion and runner-up trophies after Sunday's singles final.
Justine Henin posed with her trophy on her new Porsche after winning the singles final on Sunday.
Anke Huber, a former world No.4 and now Operating Tournament Director in Stuttgart, at the trophy ceremony.
Justine Henin took a victory lap around Center Court in her new Porsche after winning the singles final.