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The Centaur was the disguise of Susie Smythe.
Physical appearance
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Personality
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Powers and abilities
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History
What's New, Scooby-Doo?
Season two
Daphne Blake's plan was to scare the Centaur by using mythological creature costumes and dressed herself as a Gorgon, Fred Jones dressed himself as a Minotaur, Velma Dinkley dressed herself as a Hydra, Shaggy Rogers dressed himself as a Cyclops, and Scooby-Doo dressed himself as a Cerberus in order to unmask the Centaur.
The group discovered that the Centaur was actually Lysander Demas's assistant Susie Smythe who used the Centaur disguise in a plot to make Atlantis her discovery. (It's All Greek to Scooby-Doo)