Unzue is one of the two leading candidates to succeed Luis Enrique, who announced this month he will leave at the end of this season, along with Athletic Bilbao coach Ernesto Valverde.
Valverde's knowledge of Barca and his many years of experience of coaching in Spain saw him pip Argentine Jorge Sampaoli and Luis Enrique's assistant Juan Carlos Unzue to the top job.
Lionel Messi scored twice as King's Cup holders Barcelona moved comfortably into the quarter-finals by thrashing Celta Vigo 5-0 at the Nou Camp in their last 16 second leg game on Thursday.
La Liga leaders Barcelona were held to a 2-2 home draw by Celta Vigo on Saturday as their former assistant coach Juan Carlos Unzue dented the title hopes of the Catalans, who dropped points for the second game in a row for the first time this campaign.
Real Madrid are on the verge of reaching the King's Cup quarter-finals after winning 3-0 at Numancia on Thursday while holders Barcelona still have work to do after being held to a 1-1 draw at Celta Vigo.
Barcelona coach Luis Enrique is ready for surprises when he comes up against Pep Guardiola's Bayern Munich on Wednesday in what he believes will be an open and attractive game.
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Underlying tensions mean Luis Enrique will not be remembered with the same reverence as Pep Guardiola, even though he has delivered a similar trophy haul.
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