Electron beam processing is one of the effective methods for modification of surface material properties. Influence of electron beam irradiation on the structure of polymeric materials such as polyvinyl alcohol and polylactic acid was investigated. Electron beam processing was carried out at 8 kV accelerating voltage and a pressure of 3 × 10-2 Torr, the emission current was from 25 to 40 A, the pulse duration was from 150 to 300 μs and the pulse number was from 1 to 10. The elemental composition and the structural state of the surface of irradiated polymer materials were studied by infrared spectroscopy (IR-spectroscopy), X-ray photoelectron spectroscopy (XPS), scanning-electron microscopy (SEM) and atomic-force microscopy (AFM) methods. It was established that certain chemical processes take place and some physicochemical properties change under electron treatment.