New blend system of quaternized polysulfone/polyvinyl alcohol was investigated, as to its optical and electronic properties. Optical properties were analyzed by refractivity and transmission spectra. In order to obtain optical parameters, an approach proposed by Tauc for amorphous semiconductors was used, because of the similarity of the absorption edges. At the same time, the frequency-dependent-dielectric properties and conductivity of these blends were studied. The dielectric constant takes low values for the studied blend, being dependent on the chemical characteristics of the blend compounds. The dielectric loss behavior exhibits two types of relaxation, gamma and beta, for the analyzed samples, being due to temperatures at which the two processes occur in the case of pure components. The results obtained from conduction studies showed that the conduction mechanism in the quaternized polysulfone/polyvinyl alcohol blend was based on the electronic hopping process, which can be explained in terms of band conduction mechanisms, through band gap representation. The outcomes of this work highlight the importance of new polymer blends for better electrical performances. (C) 2016 Elsevier B.V. All rights reserved.