And the Blues have been tipped to sign Athletic Bilbao goalkeeper Kepa Arrizabalaga.
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The west London club completed a world-record deal for the 23-year-old last night and he will train with his new team-mates today.
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Courtois signed for Chelsea from Genk in the summer of 2011 and immediately went on loan to Atletico Madrid, where he won a La Liga title, the Europa League and the Copa del Rey as well as reaching a Champions League final in three seasons working under Diego Simeone.
Real Madrid have confirmed that Courtois will undergo a medical on Thursday morning, before signing a six-year deal and being presented at 1pm local time.
"His long-term contract reflects the belief we have in him and we look ahead to the coming seasons with an enormous sense of optimism".
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"Chelsea and Real Madrid have tonight agreed terms for the permanent transfer of Thibaut Courtois subject to the agreement of personal terms and passing a medical", Chelsea signalled in a statement published on the club's official website.
Manchester United legend Gary Neville believes Chelsea will miss Thibaut Courtois.
Kepa, who came close to joining Real Madrid in January, becomes the world's most expensive goalkeeper, his fee surpassing the 67 million euros Liverpool splashed out for Roma's Alisson last month.
Athletic do not negotiate when it comes to selling their top stars because they limit themselves to only signing Basque players, meaning the only way Chelsea can bring Kepa to Stamford Bridge is by activating his buyout clause.
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Chelsea coach Maurizio Sarri praised Arrizabalaga on Tuesday night.