The interfacial chemistry and composition of Pt electrodes sputter deposited on bromine-etched CdZnTe surfaces was studied by X-ray photoelectron spectroscopy. The interfacial composition of a functioning and a nonfunctioning CdZnTe detector shows significant differences. The degree of cation out-diffusion into the Pt overlayer and the in-diffusion of Pt into the CdZnTe correlate with the degree of oxidation found at the metal-semiconductor interface. Most of the oxide present at the interface was found to be TeO2. The results suggest that the interdiffusion of the atoms and associated charges contribute to stoichiometric variations at the metal-semiconductor interface and influence the electrical performance of the devices.