World No.1 Djokovic, who had won the last three Grand Slam titles in a 26-match winning streak dating back to the quarterfinals here last year, lost 2-6, 6-3, 5-7, 7-5, 5-7 in a marathon semifinal which started on Friday and ended on Saturday, delaying the women's final.
Djokovic, who had not dropped a set in the tournament, thus failed to hold all four Grand Slams for the second time, like he did here in 2016.
Thiem will now seek revenge on Nadal after losing last year's summit clash to the ace Spaniard in straight sets. Nadal on Friday beat Swiss legend Roger Federer 6-3, 6-4, 6-2 at the Philippe-Chatrier Court in the 39th meeting between the two stalwarts.
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