Switzerland, who are the defending champions, remain favourites with matches to come against Roger Federer and Belinda Bencic a repeat of the 2018 final.
Zverev, ranked fourth and playing in his fourth successive Hopman Cup, then secured the tie for the Germans with a 6-4, 6-3 win over Matthew Ebden.
Federer was a dominant figure in an extraordinary doubles match as the Swiss claimed the abbreviated format 4-0, 1-4, 4-3 (5/4) to clinch the title despite Germany having two match points.
The 20-time Grand Slam champion was in scintillating form as he dispatched World No.4 Alexander Zverev in straight sets 6-4 6-2 on Saturday, Xinhua news agency reported.
This year's Hopman Cup had record attendance and also featured the never-before-seen matchup between 37-year-old GOAT's Federer and Serena Williams in another mixed doubles match.
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Swiss pair Roger Federer and Belinda Bencic have won Perth's Hopman Cup defeating Germany in the final.
The crowd was appreciative of Switzerland's achievement but Zverev roasted Federer when given his chance with the microphone at the trophy presentation after the tie.
The young female star Sakkari, before one of Federer's serves, jokingly yells out the question "left or right?" refering to where on either side of her would Federer serve the ball.
"I didn't give myself much of a look in on return games and also just one poor service game in the first set - there wasn't really much in it in the end".
When asked to reflect on his incredible achievement, Federer said: "I'm very happy about these records, but I didn't come here for that".
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Zverev had a glimmer of hope in the first game of the second set, 0-30, and two deuces, but the Federer serving was just too good.
After the match, Federer said his aim for the game was to win points from serve volleys and that worked out for him. I have been writing about tennis for the last 4 years. But in the end, the experience and athleticism of Kerber proved just enough to seal the match, 7-6 (6), with a final victor.
"I'm happy I'm feeling this good and playing as well as I am", Federer said.
Team Switzerland loves the Hopman Cup.
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