AbstractTo understand the interfacial bond formation between polycarbonate (PC) and magnetron‐sputtered metal nitride thin films, PC | X interfaces (X = AlN, TiN, (Ti,Al)N) are comparatively investigated by ab initio simulations as well as X‐ray photoelectron spectroscopy. The simulations predict significant differences at the interface as N and Ti form bonds with all functional groups of the polymer, while Al reacts selectively only with the carbonate group of pristine PC. In good agreement with simulations, experimental data reveal that the PC | AlN and the PC | (Ti,Al)N interfaces are mainly defined by interfacial C─N bonds, whereas for PC | TiN, the interface formation is also characterized by numerous C─Ti and (C─O)─Ti bonds. Bond strength calculations combined with the measured interfacial bond density indicate the strongest interface for PC | (Ti,Al)N followed by PC | AlN, whereas the weakest is predicted for PC | TiN due to its lower density of strong interfacial C─N bonds. This study shows that the employed computational strategy enables prediction of the interfacial bond formation between PC and metal nitrides and that it is reasonable to assume that the research strategy proposed herein can be readily adapted to other organic | inorganic interfaces.