The generation of permanent high-grade conducting layer on the surface of polyvinylidene fluoride (PVDF) was induced by 248 nm KrF excimer laser irradiation. The results of XPS and FTIR spectra indicated that the photochemical reaction was occurred on the surface of samples and the microstructure was changed by laser light to generate HF gas,then resulted in high-stability and high-uniformity conducting layer on the surfaces. After analyzing and calculating the relationship between laser processing parameters and surface conductivity,the laser energy density of 44-112 mJ/cm2 was determined. The conductivity of the changed surfaces was increased to 12 orders of magnitude which reached to 10-1 Ω-1·cm-1. Based on the discovery of conducting layer,the mechanism of electrical conduction on PVDF surface was discussed.