Among the various nanostructural morphologies, nanofibers have a distinct interest due to the long axial ratio which strongly modifies the photocatalytic activity. In this work, study of the effect of CdO-doping on the photoluminescence properties of ZnO nanofibers was carried out. Nanofibers composed of the two oxides (ZnO and CdO) were prepared using facile, effective, simple and high yield technique; electrospinning. Typically, a sol-gel consisting of poly(vinyl alcohol), cadmium acetate and zinc acetate was electrospun. Calcination of the produced nanofibers in air did not affect the nanofibrous morphology and led to produce ZnO/CdO alloy nanofibers. Interestingly, variation of Zn to Cd ratio in the original electrospun solution did not influence the morphology, so nanofibers having CdO of 39.4, 56.5 and 72.2 wt% could be prepared. Optical properties study indicated that addition of CdO to ZnO decreases the band gap and consequently the introduced nanofibers can be utilized as photocatalyst under a visible light radiation. Moreover, the results indicated that increasing the CdO content causes to increase the solid solubility. Accordingly, the low content CdO nanofibers (39.4 wt%) reveal two band gaps in the PL spectra. Consequently, these nanofibers have the best photocatalytic activity among the prepared samples; the methylene blue dye was completely eliminated within 4.5 h. However, full dye degradation was obtained at relatively longer times when the other formulations were utilized. Beside the simplicity and low cost aspects in the proposed preparation strategy, utilizing the solar radiation as activation energy to initiate the photoreactions might recommend the introduced nanofibers to be exploited as photocatalyts in the field of waste water treatment. (C) 2012 Elsevier B.V. All rights reserved.