Copper phthalocyanine films have been deposited by glow-discharge-induced sublimation. The films have undergone postdeposition heat treatments in air at 250 and 290°C for different times, ranging from 30 min to 14 h. The properties of as-deposited and heated films have been investigated by different techniques in order to determine the effects of heat treatments on the film properties. Fourier transform infrared analysis and UV-visible optical absorption analysis point out a gradual evolution of the film structure from a mixture of α and β polymorphs to the only β polymorph in the sample heated at 290°C for 14 h. A pronounced decrease of carbon and nitrogen atomic percentages against an oxygen increase in the heated films are shown by ion beam analyses (Rutherford backscattering spectrometry and nuclear reaction analysis) and X-ray photoelectron spectroscopy (XPS). X-ray absorption spectroscopy and XPS indicate that part of the copper phthalocyanine molecules decompose during heat treatments and the formation of copper oxide takes place. The replacement of copper phthalocyanine by copper oxide in the heated films accounts for the change of their surface electrical conductance and of their electrical response to NO 2. © 2006 American Chemical Society.