The top 10 pair, beaten finalists in the previous edition of the tournament, were too good in their singles matches against Garbine Muguruza and David Ferrer.
Just over two weeks out from the year’s first Grand Slam, Kerber edged past Muguruza in three sets to open the tie, while a misfiring Zverev was given a scare by the veteran Ferrer before also winning in three.
In the dead mixed doubles rubber, the Germans made it a clean sweep with a straight sets win.
Kerber won all four of her singles matches without dropping a set at the last Hopman Cup, as part of a 14-match winning streak that was only snapped in the Australian Open semi-final by Simona Halep.
That proved to be the start of a productive year for a resurgent Kerber, who won at Wimbledon and climbed back to number two in the world.
Hoping for a similar start to the new season under new coach Rainer Schuttler, Kerber took the first set against Muguruza comfortably in the battle of the two former world number ones.
However the Spaniard wasn’t going to let her own five-match winning run against the German go easily, and took the second set.
A break of serve in the fourth game of the third set was enough to ensure Kerber maintained her perfect record in Perth, winning 6-2, 3-6, 6-3.
Kerber conceded Muguruza had proven a historically difficult opponent and she was pleased to begin her Australian Open preparation with a win.
“The first match you never know how you will feel on court,” she said.
“I was trying to find the rhythm and I am very happy about how I played.
“I was trying not to think about the head to head.”
Zverev started well against Ferrer and cruised through the first set, but then grew increasingly frustrated with his own game as the determined Spaniard fought back, breaking the German’s serve with a sublime forehand passing shot in the 10th game to claim the second set.
There was little between the pair in the third set until Zverev surged in the tiebreak to take the match 6-4, 4-6, 7-6 (7/0).
Although Zverev is ranked fourth in the world and Ferrer 126th, the German said he expected nothing less from the Spaniard, who has retired from Grand Slam tennis.
“He is the greatest fighter, maybe we have ever seen in tennis,” Zverev said.
Zverev received attention for a right leg problem during the mixed doubles, but played out the match without apparent discomfort.
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