The use of natural bitumen for waterproofing, and as an adhesive dates at least to the fifth millennium BC, with a crop storage basket discovered in Mehrgarh, of the Indus Valley civilization, lined with it. By the 3rd millennium BC refined rock asphalt was in use in the region, and was used to waterproof the Great Bath in Mohenjo-daro.
In the ancient Near East, the Sumerians used natural bitumen deposits for mortar between bricks and stones, to cement parts of carvings, such as eyes, into place, for ship caulking, and for waterproofing. The Greek historian Herodotus said hot bitumen was used as mortar in the walls of Babylon.
The  long Euphrates Tunnel beneath the river Euphrates at Babylon in the time of Queen Semiramis () was reportedly constructed of burnt bricks covered with bitumen as a waterproofing agent.
Bitumen was used by ancient Egyptians to embalm mummies. The Persian word for asphalt is moom, which is related to the English word mummy. The Egyptians primary source of bitumen was the Dead Sea, which the Romans knew as Palus Asphaltites' (Asphalt Lake).
In approximately 40 AD, Dioscorides described the Dead Sea material as Judaicum bitumen, and noted other places in the region where it could be found. The Sidon bitumen is thought to refer to material found at Hasbeya in Lebanon. Pliny also refers to bitumen being found in Epirus. Bitumen was a valuable strategic resource. It was the object of the first known battle for a hydrocarbon deposit – between the Seleucids and the Nabateans in 312 BC.
In the ancient Far East, natural bitumen was slowly boiled to get rid of the higher fractions, leaving a thermoplastic material of higher molecular weight that, when layered on objects, became hard upon cooling. This was used to cover objects that needed waterproofing, such as scabbards and other items. Statuettes of household deities were also cast with this type of material in Japan, and probably also in China.
In North America, archaeological recovery has indicated that bitumen was sometimes used to adhere stone projectile points to wooden shafts. In Canada, aboriginal people used bitumen seeping out of the banks of the Athabasca and other rivers to waterproof birch bark canoes, and also heated it in smudge pots to ward off mosquitoes in the summer. Bitumen was also used to waterproof plank canoes used by indigenous peoples in pre-colonial southern California.