The purpose of the study was to observe whether conventional porcelain firings had an effect on the underlying microstructure of cobalt-chromium alloys used in porcelain-fused-to-metal systems. One as cast (non-veneered) and two porcelain veneered Co-Cr specimens layered with and without tungsten(W)-metal conditioner were manufactured and analysed. Electron backscatter diffraction was used to determine the crystal structures and grain size across the porcelain-fused-to-metal interface. No difference was found in the microstructure of the alloy in both with and without W-metal conditioner. For the porcelain fired specimens, disparately sized granular structures were observed adjacent to the metal-porcelain interfaces compared to the bulk of the metal. Ellipsoid shaped grains at the alloy surface ranged between 1-11 μm in diameter and averaged 2.70 μm (SD: 2.17 μm) for the specimen layered with W-metal conditioner and 2.86 μm (SD: 1.85 μm) for the specimen layered without W-metal conditioner. Grains located in the bulk were > 200 μm with dendritic-like features. The depth of the fine grain structure adjacent to the surface had an average depth of 15 μm. The crystal structure of the surface layer was found to be predominantly hexagonal close-packed whereas the underlying bulk was a mixture of both face-centered cubic and hexagonal close-packed phases. For the as cast specimen, similar large grains of over 200 μm was observed but exhibited no dendritic like features. In addition, no fine grains were observed at the surface region of the as cast alloy. Conventional porcelain firings altered the interfacial and bulk microstructure of the alloy while the presence of the W-metal conditioner had no influence on the underlying alloy microstructure.