Argentina-born Di Stefano had been in a coma at the Gregorio Maranon Hospital in Spain after having been resuscitated on a Madrid street by paramedics following a heart attack on Saturday.
Di Stefano, a diabetic, underwent a quadruple aorta-coronary bypass with a pacemaker implanted in December 2005 after suffering a myocardial infarction. He had also been hospitalised several times in recent years to monitor his heart condition.
Dubbed “La Saeta Rubia” (“The Blond Arrow”) for his speed, Di Stefano is a former Argentina forward who helped Madrid win five straight European Champions Cups from 1956-60, and eight Spanish league titles. He was voted European player of the year in 1957 and 1959.
He retired at the age of 40 in 1966, ending a 22-year playing career in which he had also represented Colombia and Spain at international level.
Tributes following his death came in from several Spanish clubs and La Liga players following the news on Monday.
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