New evidence is reported here using transmission electron microscopy, scanning electron microscopy, and laser reflectance for the nature of the black glossy decoration layer present on the Attic black or red figure vases of the sixth to fourth century BC. The black layer, of total thickness about 20 μm, consists mainly of poly crystalline magnetite (Fe3O4) particles of dimensions from 0.2 μm down to extremely fine sizes embodied in an amorphous vitreous matrix. On the outer surface of the black paint we discovered for the first time a thin clear glassy film of approximate thickness 0.1 μm which is rich in Al and Fe and poor in Si. This film must be responsible for the characteristic sheen of the surface. This is verified with the reflection of laser light mostly in specular direction, a unique property compared with black paints of other areas and other periods.