Kontaveit, who has only won last year's Hertogenbosch title on the WTA tour and is currently 29th in the WTA rankings, fought back against Williams to win 3-6, 6-3, 6-2 on Saturday, reports Efe.
Williams, a finalist in Madrid in 2010, when she lost to the French Aravane Rezai, has not won a match on the clay courts in Madrid since 2012.
She hasn't played in Madrid since 2015, when she was beaten by Victoria Azarenka in her first game. On her return this year she came up against a competitive rival in Kontaveit, who went from strength to strength during the match clinching her first ever win against Williams. Kontaveit lost against Venus at the 2016 Roland Garros and at the 2015 US Open.
Kontaveit will be up against the winner in the second round of the match between Danielle Collins from the USA and Aliaksandra Sasnovich from Belarus.
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