The British No1 had never won so much as a set against the 12-time Grand Slam champion in their three previous meetings.
This time, though, Edmund showed his quality and growing maturity by dispatching Djokovic 6-3 2-6 6-3, as Ronaldo and Luka Modric enjoyed the Spanish sunshine.
The Serb is still not at his best after having surgery on a long-standing elbow problem earlier this year.
But Edmund, who is currently at a career-high ranking of world No22, took full advantage of Djokovic’s mistakes.
He played some powerful, intelligent tennis on his way to earning a third-round clash with Belgium’s David Goffin.
Edmund roared through the opening set in 31 minutes, breaking the Serb’s serve on three occasions.
But the former world No1 hit back at the start of the second and soon levelled the match.
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The decider went with serve until the eighth game when a bad bounce brought up a break point for the Brit and he converted.
Edmund then held his nerve to serve out the match in style.
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