Interfacial bond formation during sputter deposition of metal‐oxide thin films onto polycarbonate (PC) is investigated by ab initio molecular dynamics simulations and X‐ray photoelectron spectroscopy (XPS) analysis of PC|X interfaces (X = Al2O3, TiO2, TiAlO2). Generally, the predicted bond formation is consistent with the experimental data. For all three interfaces, the majority of bonds identified by XPS are (C─O)─metal bonds, whereas C─metal bonds are the minority. Compared to the PC|Al2O3 interface, the PC|TiO2 and PC|TiAlO2 interfaces exhibit a reduction in the measured interfacial bond density by 75 and ∼65%, respectively. Multiplying the predicted bond strength with the corresponding experimentally determined interfacial bond density shows that Al2O3 exhibits the strongest interface with PC, while TiO2 and TiAlO2 exhibit ∼70 and ∼60% weaker interfaces, respectively. This can be understood by considering the complex interplay between the metal‐oxide composition, the bond strength, and the population of bonds formed across the interface.