The Otzi the Iceman find indicates clothing was made of a variety of leathers for different purposes, and colors. His shoe soles were bearskin. The uppers were softer deerhide. His shirt was sewn in stripes of light and dark leather. He wore a loincloth with separate leggings, as some Native Americans did until quite recently. He had a woven grass cape.
There’s considerable evidence that string and netting dates back to the paleolithic, and woven clothing to the early neolithic. Flax is documented earlier than wool, but both exist several thousand years ago.