A heterojunction of poly(4-methylstyrene) and ZnTe was prepared on a glass substrate coated with SnO2. ZnTe was deposited by a semiclosed space technique (SCST), while a pure and iodine (1% wt)-doped polymeric layer was deposited, on the front surface of the ZnTe film, by the spin-coating method. The junction characteristics are discussed in view of the morphological surface of ZnTe obtained at different substrate temperatures and UV absorption spectra. The photovoltaic parameters were explored from current-voltage (I-V) measurements under dark and illumination conditions. The results were interpreted according to the formation of the rectifying junction at the polymer-semiconductor interface. A rectifying heterojunction and a photovoltaic effect are improved for the iodine-doped polymer layer and a substrate temperature of 350 degreesC.