Paint was one of the earliest arts of humanity. Some cave paintings drawn with red or yellow ochre, hematite, manganese oxide, and charcoal may have been made by early Homo sapiens as long as 40,000 years ago. Paint may be even older. In 2003 and 2004, South African archeologists reported finds in Blombos Cave of a 100,000-year-old human-made ochre-based mixture that could have been used like paint. Further excavation in the same cave resulted in the 2011 report of a complete toolkit for grinding pigments and making a primitive paint-like substance.

Interior walls at the 5,000-year-old Ness of Brodgar have been found to incorporate individual stones painted in yellows, reds, and oranges, using ochre pigment made of haematite mixed with animal fat, milk or eggs.

Ancient colored walls at Dendera, Egypt, which were exposed for years to the elements, still possess their brilliant color, as vivid as when they were painted about 2,000 years ago. The Egyptians mixed their colors with a gummy substance and applied them separately from each other without any blending or mixture. They appear to have used six colors: white, black, blue, red, yellow, and green. They first covered the area entirely with white, then traced the design in black, leaving out the lights of the ground color. They used minium for red, generally of a dark tinge.