This is actually a tough question and no one knows for sure! It is most likely that Copper (Cu) was the first found by humans, since the oldest existing sample we have is from 6000BCE and it was most likely used as early as 9000BCE.
In terms of what the first element to be chemically discovered was, it is Phosphorous (P). Phosphorous was first isolated from urine in 1669 by Mr Hennig Brand, a German alchemist.
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