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Goals from Marcus Joseph, Faisal Ali, Brandon Vanlalremdika and Nikola Stojanovic made sure the Black Panthers quest for a third Durand title remained on course.
The victory follows on the heels of Zverev winning the men's singles gold medal at the Tokyo Olympics.
Medvedev was top seed and favourite to take the title but was beaten for the first time by Rublev after crashing into an on-court camera and knocking it to the ground while chasing the ball at the baseline in the second set.
Humbert stepped up his Wimbledon preparations by producing a clinical display, winning 85 per cent of his first-serve points and hitting nine aces to extend his perfect record in ATP tour finals to 3-0.
The 29-year-old, who reached a career high ranking of 16th in 2019, defeated Spain's former top-10 player Roberto Bautista Agut 7-6(5), 6-2 in the final.
World No. 1s Ash Barty and eight-time champion Novak Djokovic will lead the fields at the Grand Slam slated to be held from February 8-21.
The Spaniard beat defending champion Stefanos Tsitsipas 6-4, 4-6, 6-2 in the last round-robin match in the London Group.
The world No. 3 struck 37 clean winners to claim his second round-robin victory and reigning champion Stefanos Tsitsipas's narrow defeat of Andrey Rublev later guaranteed the Austrian a semifinal spot with a match to spare.
Medvedev's 6-3, 6-4 win over Zverev put him joint top of the Tokyo Group alongside world No. 1 Djokovic, who put on a masterclass to trounce debutant Schwartzman 6-3, 6-2.
Austrian Dominic Thiem got his campaign off to a fine start with a 7-6(5), 4-6, 6-3 victory over Stefanos Tsitsipas.