Discovered and named by Albin Weisbach in 1886,[4] it is of interest as it was the material from which Clemens Winkler isolated the element germanium, 15 years after it had been postulated by Mendeleev.

It was first described for an occurrence in the Himmelsfürst Mine, Ore Mountains, Freiberg, Saxony, Germany.

[5] Isomorphous with argyrodite is the corresponding tin bearing mineral Ag8SnS6, also found in Bolivia as pseudocubic crystals, and known by the name canfieldite.

Argyrodite gets its name from the Greek words that loosely translate into "rich in silver".

[6][7] They are considered to be of the form: Li7-xBCh6-xXx With x between 0 and 1, B denoting either phosphor or arsenic, Ch for sulfur or selenium and X for chlorine, bromine or iodine.