Cationic polysulfones containing quaternary ammonium side groups (PSFQ), synthesized by reaction of the chloromethylated polysulfone (CMPSF) with a tertiary amine, N,Ndimethylbutylamine (DMBA), are considered to be suitable for a wide range of applications from the electronic field. Additionally, quaternized polysulfone-based composites with optical and electrical properties represent a challenge for researchers. Therefore, it is of interest to find out whether PSFQ can be designed for specific applications in blends with polyvinyl alcohol (PVA) and to establish their impact on the different properties. Thus, in the present study the cationic polysulfone PSFQ was analyzed in combination with PVA, which is supposed to improve among the other properties, such as hydrophylicity, flexibility, and the optical ones [1].In this context, the thermoplastic characteristics (e.g.,the refractive index and dielectric constant)were evaluated using the structural and topological techniques of spatial arrangement of the constituent atoms from analyzed polymer [2], by means the zero-order connectivity indices and first-order connectivity indices