Serena's demolition of Elena Vesnina in the day's first semi-final had set up the prospect of a first all-Williams Wimbledon final since 2009.
But Kerber had no intention of being a footnote in Wimbledon history and she saw off five-time champion Venus in 71 minutes on Centre Court to reach her first All England Club title match.
"Venus won so many times here and was playing really well. That's why I'm so happy to reach my first Wimbledon final," Kerber said.
Kerber stunned Serena to win her maiden Grand Slam crown in the Australian Open final in January and the 28-year-old again stands in the way of the world number one's bid to win a record-equalling 22nd major.
Having beaten one Williams, the fourth seeded Kerber can set her sights on becoming the first player to defeat both of the American siblings in the same Grand Slam since Kim Clijsters at the 2009 US Open.
"It's a completely new tournament and surface. I will just try to go out with a lot of confidence and play my best tennis," Kerber added.
Kerber couldn't be in better form heading into Saturday's final.
She had raced through her six matches at Wimbledon without dropping a set, now has WTA tour-best 34 match wins in 2016 and is guaranteed to rise to a career-high second in the world rankings next week.
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