The former Spain international made 40 appearances for Besiktas in a 16-month spell before his retirement in 2012.
"Today I want to thank Real Madrid my home, for all the years that I enjoy as a footballer and as a coach," Guti said on his official Instagram account.
"I will join in a few days Besiktas as a second coach to continue growing professionally.
"I am grateful to Besiktas for the love and trust that you have placed in me, I will return it to you with a lot of work and enthusiasm."
(Reporting By Arnab Paul in Bengaluru)
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