The Stone Age was a prehistoric period during which stone was widely used in the manufacture of implements with a sharp edge. It was proceeded by the Bronze Age.
In 2267, Lindstrom described the Beta III Lawgivers as "a bunch of Stone Age characters running around in robes". (TOS: "The Return of the Archons")
In 2365, Jean-Luc Picard commented that Humans with 24th century technology would appear magical to Stone Age people. (TNG: "Contagion")
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