Either after passing away in the White Room or by accident when they were trying to retrieve him from ANHS Ayanokouji meets the Goddess Eris and chooses to reincarnate in the world of Konosuba and chooses a good ability to take with him. He will enter the world a short time after Kazuma and Aqua arrive.
Suppose Kiyo will want to live a peaceful life here and might get curious and want to travel since he's free.
Due to his past life his stats will be very good and let him do pretty much any job. Though you could possibly have his stats appear average and have his true abilities hidden.
Not sure if you'd want to involve him with Kazuma's party or not since I'm sure it certainly wouldn't be peaceful.
Perhaps having him befriend Yunyun and Wiz could be an idea. Something like adventuring with Yunyun mainly and only really going with Kazuma's party for big quests that require a lot of people.
He could get involved with Kazuma and Vanir's business and also earn enough money that he can live peacefully.
Though I said about not having him involved too much with Kazuma's party. The idea of Kiyo awakening his inner sadist because of Darkness certainty doesn't sound bad.
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IDEAS FOR COTE & OREGAIRU WRITERS
RandomCollection of Classroom of the Elite and Oregairu ideas I wouldn't be able to write myself and are free for the taking. There will be oneshots and things that could potentially be fleshed out a bit more. Hopefully some of these ideas could help insp...