Abstract The photoconductivity and fluorescence spectra of poly(N-vinylcarbazole) (PVCz) films doped with various materials were investigated. The photoconductive properties of doped films may be grouped into three classes according to the kind of dopant. The doping of an electron donor, such as tetramethyl-p-phenylenediamine and 1,5-diaminonaphthalene, reduced the photocurrent in all the wavelength regions by a factor of 102 to 104 because of the hole-trapping effect of the dopant molecule. The exciplex formed between the donor and PVCz does not seem to contribute to the photocurrent. The doping of an acceptor, such as TCNE and dimethyl terephthalate, on the other hand, enhanced the photocurrent. The field-assisted thermal dissociation of an excited CT complex formed between PVCz and an acceptor seems to be a carrier generation process. The doping of anthracene or perylene quenched the fluorescence of PVCz by a factor of 10 to 30 and reduced the photocurrent in the UV region by a factor of 2 to 7, while it enhanced the photocurrent in the absorption region of the dopant.