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Twilight is an antichrist-esque entity that represents the consciousness of a new dimension that seeks to be "born" in order to replace the current universe.
Before the Comics
While the Twilight dimension hadn't existed in the Earth reality yet, it still had some form outside the universe, and it was prophesised that a Slayer who changed the balance of the world would birth the new Twilight universe, which would subsequently destroy and replace the old one. It was a prophecy so feared that some Watchers committed suicide in fear of its inevitable coming.
At the time the series takes place, it was one of the plans of the Wolfram and Hart law firm for the apocolypse, but they also learned to fear it.
Begining the prophecy
At the time of the comics, the prophecy was set in motion, and as it turns out Buffy Summers was a chosen slayer for the prophecy. To serves as the "Yin to her Yang", Twilight chose's Buffy's vampiric ex boyfriend Angel for this purpose.
The disembodied Twilight's entity manipultates Angel telling him the world will be destoryed if he doesn't help stop the Buffy and her allies from leading the world to chaos. Angel fell for the lies and, in a disguise, chose to represent Twilight and shared and alliance with the Anti Slayer terrorist task force. Angel, while reluctant to decive Buffy, went through with the plan with various unsuspecting minions, including some of Buffy's previous enemies.
Being resposnible for much of the drama in the comics, at the climax of the arc, during a battle between "Twilight's" forces and Buffy's allies in Tibets mountins, Buffy's Twilight powers are acitvated. Buffy subdues and unmask's "Twilight" and discovers Angel's secret. Angel tells Buffy his motovatin and that he loves her. Angel and Buffy give into thier passions and engage in supernatural sex, which Twilight needed in order to be "conceived".
The climax of the arc inteseify's when, Angel and Buffy find themselves in the Twilight dimension where they could shape reality, while the Earth starts to fall to natural disasters and demons begin to attack. Angel contimplates staying with Buffy, but she convinces him that thier home needs them and they return to Earth.
During the battle, the Scoobies learn that in order to fully destroy and replace the Earth dimension, Twilight must take the Seed of Wonder, which is located beneath the ruins of Sunnydale and is the Earth's soul and source of all magic, and must remove it and take it as the Twilight universe's own soul. As the Scoobies head to Sunnydale, Twilight confronts Angel demanding he and Buffy finish what they started and in rage, completely possesses Angel. The possessed Angel pursues the Scoobies to Sunnydale, where Twilight infulences him to kill the resurrected Master, who was trying to protect the Seed from the Scoobies, and then Rupert Giles who was trying to destroy it. Buffy beats Angel back, before destroying the Seed of Wonder, an act which ended most forms of magic in the Earth dimension and closed it off from the other dimensions. With the Seed gone and the Earth closed off, the Twilight entity and the demons it had sent were all banished back to the Twilight dimension, unable to access Earth again, and the Twilight apocalypse was derailed.
- Despite Twilight's name and the similarities between its birth and the main plot point of the Twilight Saga (a human girl and a benevolent vampire in love), the character is in no way connected to the Twilight series. Buffy's writer Joss Whedon confirmed he came up with the characters name before he heard of the Twilight Saga.