Oviedo have appointed Carrion after the dismissal of Veljko Paunovic on Thursday.
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Paunovic had guided Oviedo to Primera promotion last season, but was axed this week with the team sitting 17th on the LaLiga table.
Oviedo haven't been seen in LaLiga for the past 24 years.
Carrion, meanwhile, is a former Oviedo coach and returns for a second stint in charge. He also had a spell leading Las Palmas in the Primera last term.