A study on the modification of the physicochemical properties of the carbon-nitrogen compounds when submitted to a thermal annealing process is reported. Original films were obtained by ArF laser ablation using organic and inorganic targets in a reactive atmosphere of ammonia or in vacuum conditions. The evolution of the film chemical composition and bonding configuration was followed by controlled thermal effusion, Fourier-transform infrared and energy dispersive x-ray spectroscopies. The thermal energy supplied to the material during the postdeposition annealing of the CN, films promotes the formation of single CN bonds although the film nitrogen concentration decreases by the effusion of hydrogen cyanide, cyanogen, and CN radicals. Additional experiments at different substrate processing temperatures were carried out in order to analyze the role of the temperature on the film properties during the film processing and during postdeposition annealing.