One of the team that made the discovery, Dr Lawrence Barham from the University of Bristol, UK, said: "We're dealing here with people who were perhaps using symbols far earlier than we expected.
The team found pigments and paint grinding equipment believed to be between 350,000 and 400,000 years old. The oldest pigments previously found were 120,000 years old and the oldest known paintings are just 35,000 years old.
Over 300 fragments of pigment have now been found in a cave at Twin Rivers, near Lusaka, Zambia. These materials were apparently gathered in from the surrounding area.
This part of Africa is often associated with the emergence of modern humans.
Yellow and purple
It is likely that the stone age inhabitants used the colours, which range from yellow to purple, to paint their bodies during hunting rituals, ceremonies and other social events.
The remnants date from before the appearance of anatomically modern humans, Homo Sapiens.
One of the team that made the discovery, Dr Lawrence Barham from the University of Bristol, UK, said: "We're dealing here with people who were perhaps using symbols far earlier than we expected.
"It also implies the use of language, so it's an important discovery, full of implications for the development of new behaviours."
Stone Age man's first forays into art were taking place at the same time as the development of more efficient hunting equipment, including tools that combined both wooden handles and stone implements.
This latest discovery adds to the evidence that the development of new technology, art and rituals played a vital role in the evolution of modern humanity.