Emery, who is under contract with Sevilla until June 2017, has been linked with several clubs in Europe, including French champions Paris St Germain and Premier League side Everton.
"Emery's intention is to, throughout this week, resolve unilaterally his contract with Sevilla FC because of his wish not to continue as coach of the first team for the 2016-17 campaign," Sevilla said in a statement.
"Following the Basque coach's irrevocable decision to terminate his contract with Sevilla FC, the club has moved to find his successor.
"Former Chile coach Jorge Sampaoli will arrive in Seville on Monday to begin talks with the club."
According to Marca, Emery will compensate Sevilla by paying two million euros (1.58 million pounds) to be released from his current contract.
The 44-year-old joined Sevilla in January 2013 and has steered the club to three straight Europa League titles.
Sevilla finished seventh in the Spanish league in the 2015-16 campaign but as Europa League champions, will play in the Champions League next season.
Sampaoli has been out of a job since resigning as Chile coach in January. He was on the three-man shortlist for the 2015 FIFA World Coach of the Year after leading his national team to the Copa America title last year, a tournament they hosted.
The 56-year-old Chilean has never coached in Europe.
(Reporting by Adriana Garcia; Editing by John O'Brien)
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