Glazed objects, mainly in the form of glazed quartz and steatite solid stones, first appeared during the fifth millennium bc. At the present time, it is generally accepted that the accidental discovery of glazing was associated with ancient copper production. However, the replication experiments already conducted on glazed stones were unable to provide a convincing explanation for the accidental invention of ceramic glazes. This paper attempts to suggest a possible explanation for the accidental invention of glazes on solid stones (i.e., steatite and quartz) during the Chalcolithic period. A series of replication experiments were undertaken and the resulting objects were examined using SEM–EDS.