The Catalan giants are looking for a new manager to succeed Luis Enrique at the end of the season.
Valverde has been heavily linked with the vacancy and reports in Spain suggested the club had made enquiries over his availability.
Luis Enrique will leave Barcelona at the end of the season
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However, a statement from the Catalan club on Friday evening read: "FC Barcelona emphatically denies having asked permission from Athletic Club to negotiate the hiring of coach Ernesto Valverde, as reported tonight on television in Catalonia.
"Likewise, the club denies that technical secretary Robert Fernandez has contacted Ernesto Valverde in recent days to negotiate joining FC Barcelona."
Barcelona deny making a move for Ernesto Valverde
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Earlier in the day, Barcelona were fined 19,000 euros for their ecstatic celebrations at the end of their stunning Champions League comeback victory over Paris Saint-Germain earlier this month.
Sergi Roberto’s 95th minute strike sent Barcelona though to the quarter-final of the competition where they will take on Juventus.