That's a rather vague question. The earliest true humans were Homo erectus. These early humans only used stones to begin with. Their earliest technology was called Oldowan and involved breaking smooth, rounded pebbles from rivers in rather a crude fashion to get a sharp edge to cut with. Later they developed a more sophisticated technique, creating a large, hand-held item shaped rather like a teardrop. It had two sharp sides coming to a point and one dull, rounded side which the person grasped. This was called a hand axe. People used these for nearly a million years across nearly the whole of the Old World. Late in their existence, these folks also developed the first spear, which was simply a sharpened wooden stake that may have been hardened by leaving it in the fire for a short while.
Later, some of these people evolved into the Neanderthals who developed what is called the Levallois technique of preparing a stone core by shearing off flakes. They used the flakes at times and at other times whittled down the core and used it. At first they held the stone points to use them. Eventually they figured out how to haft a blade onto a wooden handle, using something sticky. In some areas they used heated red ochre. In Eastern Europe, though it was apparently some sort of starchy root, as shown by microscopic examination of the stone points. They made a greater variety of points and tools. Their tool culture is generally called the Mousterian (oh, I forgot to tell you that the hand-axe culture was called the Acheulian). Late in their existence, the Neanderthals developed a whole series of transitional cultures that were more advanced including the Chatelperronian in France.
The last group to be mentioned is that of Homo sapiens, our own ancestors. They evolved from Homo erectus in Africa. They learned to make harpoons and other specialized tools not only from stone and wood but also from bone, antler, and ivory (particularly mammoth ivory, which...
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