Our knowledge on the bonding mechanisms between the metal and ceramic parts of dental systems is very limited. This work tested the hypothesis that the details of the interface processes can be described in the framework of a chemical diffusion model. The development of interfacial phases was investigated by cross-sectional analytical transmission electron microscopy between a NiCr (Wiron 99) alloy and three different dental ceramics (Carat, Vita VMK 95, and Vision). All systems were investigated at normal firing conditions (suggested by the manufacturer) and at increased firing times as well. The conclusions are based on the results that the formation of a nanocrystalline Cr(2)O(3) layer and amorphous silicon oxide inclusions were detected in the early stage of the firing process in all investigated systems, and that, in the case of Carat and Vision ceramics, formation of complex NiCr and NiCrTi oxides was also observed at longer annealing times.