Kane Williamson will captain the T20 World Cup squad for a fourth time as New Zealand hunt for a maiden title
In the White Group, Vera Zvonareva beat Kim Clijsters 6-4 7-5 while Jelena Jankovic takes on Victoria Azarenka to close out the round robin stage in Friday's final match.
The 29-year-old Dementieva, making her 10th appearance at the prestigious tournament, blinked away tears as she thanked her fans around the world and paid tribute to her mother Vera for her support throughout her career.
Dementieva and Schiavone had already been eliminated from the Maroon Group after Caroline Wozniacki and Sam Stosur sealed semi-final spots a day earlier, but with year-end ranking points and $100,000 on offer for the win neither player lacked motivation.
French Open champion Schiavone, making her singles debut at the $4.55 million season-ending tournament, suffered an early break but hit back immediately and moved into a 4-2 lead.
Dementieva broke in the seventh and then levelled at 4-4 but the 30-year-old Schiavone regained the momentum and skipped with delight after sealing the set 6-4.
The Italian upped the tempo in the second set and quickly got the measure of Dementieva¡¯s serve and wrapped it up 6-2.
World number two Zvonareva maintained her perfect record in the White Group with an impressive straight sets victory over Belgian Clijsters.
The Russian, who moments before the match bade an emotional farewell to Dementieva, was the only player to go through the group stage unbeaten and will play Wozniacki in the semi-finals on Saturday.
Clijsters will play Stosur for a place in the final.
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