In the stone age.
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I dont know how the first knife was ever made in cavemen times but I know thousands of years ago in about 1000bc - 400 AD the knives were made of nothing but flint (sharp) rocks tied to a wood handle (possibly stick) with leather.
Knives, in one form or another have been around since prehistoric times. Early man (and possibly, even apes) have used tools. There are many examples of flint scrapers used for cutting and scraping hides. The original cutters may have been naturally split flints or other hard, brittle stones but very soon (historically speaking) men were able to actually form flints to the shape that they wanted. It is even possible that Neanderthal Man had the ability to shape flints into tools. When metals (such as copper) were discovered, it was a natural progression for cutting edges to be made from these more durable materials. It was found that these materials too could be given an edge which was superior to the brittle flint edges and it could be re-sharpened. The rest, as they say, is history.
Knives were not originally made-they was found as the earliest knives were simply pieces of broken rock,flint, etc.
Primitive knives were simply sharp stones. They progressed technologically from there.