The effects of ultraviolet (UV) irradiation on the work function of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT:PSS) have been investigated in this study. Spectroscopic methods [x-ray photoelectron spectroscopy and Raman spectroscopy (532 nm excitation)] and electrical conductivity measurements were used to characterize the electrical conducting polymer PEDOT:PSS prepared by UV irradiation. The authors found that UV irradiation could lead to an increase in the work function and the enhancement of electrical conductivity of PEDOT:PSS, resulting from a decrease in the number of the charge-trapping-related defects and the formation of linear or expanded-coil conformation.