In this study, a novel procedure to increase the yield of the non-crosslinked, photoconductive, white form of linear poly(N-vilzylcarbazole) (LPVCz) is reported. The yield of LPVCz is increased (up to 53%) by the addition of catalytic amounts of eerie ammonium nitrate as an oxidant during the electrochemical polymerization of N-vinylcarbazole in a divided electrochemical cell. The concentration of Ce(IV) remained constant during the polymerization since Ce(III) is readily oxidized to Ce(IV) electrochemically. Since the electrochemical oxidation of Ce(lll) to Ce(IV) took place simultaneously at the anode, the deposition of dark green crosslinked polyvinylcarbazole on the electrode surface, which hinders the formation of white LPVCz, can be prevented. The Fourier transform infrared, ultraviolet-visible and fluorescence spectra of white LPVCz showed that the structures of polymers are the same as those produced by conventional polymerization. Copyright (C) 1999 John Wiley & Sons, Ltd.