- Jill Pole – A pupil at Experiment House who is found by Eustace Scrubb, crying, after she is bullied by a gang of children.
- Eustace Scrubb – Appeared in The Voyage of the Dawn Treader and is a cousin of the four Pevensie siblings from the earlier stories. Became a much nicer person after his brief time as an enchanted dragon in the previous story.
- Puddleglum – A pessimistic Marsh-wiggle who helps Jill and Eustace on their quest. He guides them and keeps them on track. He represents common sense and the voice of reason.
- The Lady of the Green Kirtle – The ruler of Underland, who plans to conquer Narnia with its rightful heir under her spell at her side.
- Prince Rilian – Heir to the Narnian throne, who was captured by the Lady of the Green Kirtle and enslaved in her Underworld.
- Aslan – The Lion who created Narnia; the only character to appear in every book.
- King Caspian – Elderly King of Narnia who appeared in Prince Caspian as a boy and The Voyage of the Dawn Treader as a young man; in The Silver Chair he is sad because his only son was taken from him 10 years earlier just after the death of his wife from a serpent attack.
- Glimfeather – a large talking Owl who spots Eustace and Jill during their arrival from Aslan's eastern country; he helps them by bringing them to a Parliament of Owls, where the history of Rilian is explained, and then by helping to carry them to meet Puddleglum. His speech often rhymes with the onomatopoeic call of owls, "to-whoo!"[6][7] ("There's something magic about you two. I saw you arrive: you flew."[8]).
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