Laser-electrochemical doping of poly(N-vinylcarbazole) (PVK) leads to the formation of high conducting PVK polymer. The doped polymers are characterized by IR spectra and electrical conductivity measurement. The electrochemical and laser-electrochemical measurement results show that the photochemical effect and thermal effect caused by laser irradiation of the working electrode can effectively decrease the degree of cross-linking of the polymer and thereby increase the doping degree of ClO4- counterion. The conductivity of polymers is therefore improved.