The effect of laser irradiation during the deposition process on the structure and photoelectrical, optical and luminescence properties of CdS thin films prepared by the method of chemical spray pyrolysis, are investigated. Irradiation of the films during their deposition process leads to changes of preferential orientation of the grains from the [002] axis to [101] and to a considerable increase in photosensitivity, transparency and intensity of exciton luminescence of CdS films. These changes are explained in terms of the photodissociation and photoionization of the original components and the subsequent increase of cadmium and sulphur ion mobility on the substrate surface due to the influence of incident laser radiation.