Polly Poe is Mr. Poe's wife. The Baudelaires stay with her and Mr. Poe prior to living with Count Olaf.
When the Baudelaires stay with her and Mr. Poe, she buys a lot of itchy and ugly clothing for them. Mr. Poe also adds "Call my wife!" to the list of random cries for help he utters in The Reptile Room when he thought that Sunny had been poisoned by the Incredibly Deadly Viper. At one point Mr Poe says that he will tell his wife that dark is in, indicating that she is quite a fashionable woman, or at least tries to be.