DG (Zooey Deschanel) is a small-town waitress who feels that she does not fit into her Kansas farm life and has visions of a lavender-eyed woman (Anna Galvin) warning her that a storm is coming. Her visions are realized when the sorceress Azkadellia (Kathleen Robertson), tyrannical ruler of the O.Z. (Outer Zone), sends her Longcoat soldiers through a "travel storm" to kill DG. DG escapes through the storm into the O.Z. and befriends several of its inhabitants: Glitch (Alan Cumming), who had half of his brain removed by Azkadellia; Wyatt Cain (Neal McDonough), a former "Tin Man" law enforcer who was locked in an iron suit for years as punishment for opposing Azkadellia; and Raw (Raoul Trujillo), a "viewer" whose people have been enslaved by Azkadellia. DG receives a magical symbol on her palm and learns that her Kansan parents are androids and that her real mother is the lavender-eyed woman of her visions. Visiting the Mystic Man (Richard Dreyfuss) in Central City and continuing on to the Northern Island, the group learns that Glitch was once the advisor to the Queen of the O.Z. and that DG and Azkadellia are actually sisters and the daughters of the Queen. DG remembers that Azkadellia killed her using dark magic when they were children, but their mother revived her by light magic and gave her secret instructions on how to find the Emerald of the Eclipse, which Azkadellia now seeks. Azkadellia confronts the group with her Longcoats and mobats, capturing DG and Raw. Cain fights the Longcoat captain Zero (Callum Keith Rennie) and learns that his wife and son, whom he thought Zero had killed, are still alive. Zero shoots Cain, sending him falling into a lake of ice.
Glitch rescues and revives Cain, and they journey to Azkadellia's castle to rescue DG. Azkadellia interrogates DG, learning that the Emerald of the Eclipse is protected by the "Gray Gale". The Mystic Man is killed by Azkadellia after advising DG to head south. DG is freed by a small dog who is revealed to be a shapeshifter named Tutor (Blu Mankuma), her childhood teacher who is also nicknamed Toto. DG, Glitch, Raw, and Cain head south with Tutor, not knowing that he is marking their path for Azkadellia's mobats to follow. Along the way DG rediscovers some of her magical abilities—restoring a withered fruit tree in the fields of the Papay—and Cain discovers his wife's grave. More of DG's memories return in the lake country of Finaqua: As children she and Azkadellia were very close, but that changed when DG accidentally released the spirit of an ancient, evil witch (Karin Konoval) from a cave. The sisters' magic would have protected them if they stayed together linking hands, but DG fled and the witch possessed Azkadellia. DG realizes that all of the tragedies which have befallen the O.Z. are the result of that mistake she made as a child.
The party heads farther south in search of DG's father Ahamo (Ted Whittall). Tutor's treachery is discovered but he is allowed to stay with the group in his canine form. In the Realm of the Unwanted they are led into a trap: Glitch, Raw, and Cain are captured by Zero, but are freed by resistance fighters led by Cain's son Jeb (Andrew Francis). Zero reveals the scope of Azkadellia's plan, which is to use the Emerald of the Eclipse in combination with a machine called the Sun Seeder to lock the O.Z.'s two suns in place behind the moon during an upcoming eclipse, covering the land in permanent darkness. The Sun Seeder had been designed by Glitch during his time as the Queen's advisor, and the removed portion of his brain is being used to control it. Meanwhile, DG meets Ahamo and the two travel by hot air balloon to the hidden mausoleum of the O.Z.'s royal line. DG learns that the Gray Gale is Dorothy Gale, her "greatest great-grandmother" and "the first slipper" to travel to the O.Z. from Earth. She enters Dorothy's tomb, finding herself in a black-and-white representation of her Kansas farm and receiving the Emerald from the expecting ghost of Dorothy who lives in the spirit realm. Azkadellia arrives, capturing both Ahamo and the Emerald and leaving DG trapped in asarcophagus. DG escapes using magic and is reunited with her friends, and together they infiltrate Azkadellia's fortress as she locks the suns in place. DG clasps hands with Azkadellia, freeing her from the witch's possession just as her companions reverse the Sun Seeder's pulse, destroying the witch. DG and Azkadellia are reunited with their parents as the suns emerge from behind the moon, shedding their light on the O.Z.
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