X‐ray photoelectron spectroscopy spectra measured on copper sulfide (CuxS) films showed that a thin surface reaction product containing Cu in the +2 valence state was formed on CuxS films exposed to air for 46 h at 40 °C and 90% relative humidity. An entirely different CuxS surface reaction product layer was formed in dry air at 170 °C for 30 min and it contained sulfur in the +6 valence state. The copper (Cu) valence state in CuxS was not found to be +2 even when thexvalue was less than 1.9. When the argon sputter‐cleaned surface of CuxS or CuxS/CdS films was exposed to room‐temperature air for 10 min, cadmium (Cd) atoms appeared on the CuxS surface. X‐ray powder diffraction patterns showed that CuO and CdS reacted at 500 °C in flowing nitrogen to form Cu2S and CdO. This cation exchange between CdS and copper oxide may explain the surface Cd on the CuxS films. The standard free energy of reaction between CuO and CdS is positive while that between Cu2O and CdS is negative. These results indicate a method for stabilizing CuxS/CdS solar cells against degradation.