In the Near East and Egypt, vitreous materials in the form of glazed stones and faience were first produced from about the 4th millennium B.C. Subsequently, the period around 1500 BC saw major developments in the range of vitreous materials with the production of glass vessels and glazed clay objects and an extension in the range of colorants used. This paper first describes how the examination of artifacts has been used to reconstruct the processes involved in the production of these different vitreous materials. This information is then used to try to understand how the new technologies were discovered and why they were adopted.