4.4 Mya
We’ve got earlier hominins – Sahelanthropus, Orrorin tugensis, even an earlier species of Ardipithecus – but Ardi (her nickname, her species is Ardipithecus ramidus) stands out because she left us an exceptionally complete skeleton.

And she helped to upend a lot of theories based on drawing a straight line between modern chimpanzees and later australopithecines. She was a biped. Her legs tucked under her pelvis, with a short lower spine, and a broad pelvis (all closer to modern humans than to chimps). Her outer foot was adapted for walking on the ground. But her toes were long-ish. And her big toe stood way off to the side: well-adapted for grasping branches. So when she was walking on the ground, she had to use her second toe to push off, instead of – like you and me – her big toe.
Ardi really shifted people to realizing that gorillas and chimps are specialized beasts, specialized in being big apes adept at climbing trees, grasping branches, swinging around, and pulling themselves up by their arms, but paying a price in inefficient knuckle walking when down on the ground. Ardi was taking up a different specialization, still a tree climber (her habitat was woodland, more than savannah), but ambling around (not quite striding yet) two-legged on the ground.
So the common ancestor of chimps and humans, back before Ardi, apparently didn’t look all that much like either. In some respects she might have been somewhat closer to humans. She might even have been a sometime biped on the ground.
For a great recent summary, including lots of information about Ardi, and also about the politics, academic and otherwise, of digging fossils, check out Fossil Men: The Quest for the Oldest Skeleton and the Origins of Humankind.