Greipel dominated a bunch sprint to win the sixth stage of the race, held over 176.5 km between Aix-en-Provence and Montpellier, ahead of Slovakian Peter Sagan and Britain's Mark Cavendish.
But the real story of the day was Daryl Impey, who made Tour de France history on Thursday by becoming the first African to take possession of the yellow jersey.
Impey, a South African, took over the race lead from Australian teammate Simon Gerrans.
"I'm really proud to be the first South African and the first African to wear the yellow jersey," said Impey, who had been in second place overall since Orica-GreenEdge's triumph in the team time trial on stage four.
"Sometimes all the stars line up for you and this is definitely one of those moments. To wear the yellow jersey at the 100th edition of the Tour de France is just a dream come true.
"History has been made and I'm really excited. I'm sure a lot of people back in South Africa are really happy.
"To be able to say I wore the yellow jersey for just one day is something I will treasure forever."
Britain's Cavendish, who claimed his maiden win of the 100th edition and 24th of his Tour de France career on Wednesday, finished fourth after having crashed with 34 km to race and having battled to rejoin the peloton.
"It was a very nervous stage but I knew if we kept it together we could win this stage," said Greipel, one of several sprinters out to grab a share of the glory normally enjoyed by Cavendish.
Impey, whose career was revived when he joined Orica on their inception in 2011 following an aborted move to the now-defunct Pegasus team, leads Norwegian Edvald Boasson Hagen of Sky by 3secs with Gerrans third overall at 5.
Another Orica rider, Swiss Michael Albasini, is fourth on the same time while Poland's Michal Kwiatkowski, who is wearing the white jersey for the race's best-placed rider aged 25 or under, is fifth at 6secs. Britain's Chris Froome, who is the favourite to win this year's race, remains eight seconds behind Impey and the yellow jersey.
The peloton now moves on to the Pyrenées which will provide the first real test of this year's Tour de France.