Li Na failed to complete her third round fight against Nadia Petrova due to injury while Zheng Jie lost to Justine Henin-Hardenne.
Li Na's poor serving had given her rival all the advantage in taking control of the match at the $1.3 million Rogers Cup.
The right ankle sprain forced Li Na out of the match in the middle of the second set with Petrova leading 3-0.
Another Chinese player Zheng Jie also bows out of the tournament after a loss to former world number one Justine Henin-Hardenne 6-2, 6-4 in the third round.
In other events, US Open champion Svetlena Kuznetsova who was seeded third, was ousted by Argentine Gisela Dulko in a fierce battle.
Kuznetsova lost the game due to a back injury.
Meanwhile, 2nd seed Amelie Mauresmo of France continued her strong performance defeating Conchita Martinez from Spain 6-0, 6-2. She will face Petrova in the quarter-finals.
(CRI August 19, 2005)