Goals from Lukas Podolski, Miroslav Klose, Thomas Mueller and Brazil-born striker Cacau left Germany on top of Group D Sunday.
Ghana are second in the section having beaten Serbia 1-0 in the day's other game, a victory which delivered Africa's first win in the first World Cup staged on the continent.
Slovenia saw off Algeria 1-0 to go top of Group C, ahead of England who had been held to a 1-1 draw on Saturday.
Germany's victory was particularly sweet for Klose, the top scorer in the 2006 tournament, who took his career World Cup finals tally to 11.
Australia's miserable night in Durban was compounded by having Everton star Tim Cahill red-carded in the second half.
"Everything worked well and it is important that things went well in the first game," Klose said.
"We have earned some respect. You could see that we had fun playing football out there. I know what I can do. I feel great."
Ghana converted a late penalty to edge Serbia 1-0 in a tense Pretoria showdown while goalkeeping howlers continued in Group C as Algerian Faouzi Chaouchi joined Robert Green of England in the hall of shame by gifting Slovenia a 1-0 win in Polokwane.
Striker Asamoah Gyan sent Vladimir Stojkovic the wrong way from an 85th-minute spot kick after Zdravko Kuzmanovic handled a cross and the Black Stars collected three points that could pave the way to a second-round spot.
Serbia were reduced to 10 men earlier when centreback Aleksandar Lukovic tugged the shirt of a rival and received a second booking followed by a red card.
Ghana goalkeeper Richard Kingson made a superb block from a point-blank Milos Krasic drive as the match exploded into action at a packed Loftus Versfeld stadium.
"Everyone is happy, not only in Ghana but the whole of Africa," Gyan said. "I'm so happy, not for Ghana winning but for an African team winning in the World Cup. It's not so easy.
"We knew all Africa would support us. I really drove off that."
Slovenia captain Robert Koren could hardly believe his luck 11 minutes from full-time when Chaouchi allowed a tame, curling shot from outside the penalty area slip into the corner of the net.
The gift-wrapped goal followed an even worse blunder by Green late on Saturday as he presented United States striker Clint Dempsey with an equaliser in a 1-1 draw.
It was the first Slovenian World Cup victory after three losses eight years ago and gave them a two-point lead over the favoured English, and the Americans.
Algeria looked slightly sharper for much of a match watched by former France star Zinedine Zidane only to play the last 17 minutes a man short after substitute striker Abdelkader Ghezzal was sent off for a second caution.
"Even before the match, we had said that our target was to reach the second round, and this win will only boost our confidence in ourselves," said Koren.
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