When the poly vinylidene fluoride (PVDF) disk is irradiated by the laser with wavelength of 248 nm, the surface electrical conductivity of the sample is increased nine orders of magnitude to 10-4 (Ω·cm)-1 and the electrical conductivity of initial sample before laser irradiation is 10-13 (Ω·cm)-1. With adjusting the laser energy density, the gas atmosphere, the pulse frequency and the number of laser shots, the optimal technological conditions of the laser irradiation was obtained. Based upon the analysis of X-ray diffraction, Raman spectroscopy and micrographs of the samples, we conclude that laser breaks the C-F bond leaving graphite on the surface of the samples which lead to the transition from an insulator to a conductor.