Early vitreous materials (i.e. Glazed stone, faience, frit and Egyptian blue) which were used in Egypt and Mesopotamia from the 4th millennium BC onwards to produce small objects are characterized in terms of their chemical composition and microstructure as determined by examination in a scanning electron microscope with attached energy dispersive spectrometer. Having thus established their microstructural and mineralogical differences, the possibility of distinguishing between these early vitreous materials either by careful visual examination supplemented with x10 magnifying glass or by x-ray diffraction analysis of a very small sample is demonstrated.