Quaternized polysulfones were synthesized by the quaternization reaction of chloromethylated polysulfone with different tertiary amines −N,N‐dimethylethylamine (DMEA) and N,N‐dimethyloctylamine (DMOA), respectively. New blends from these quaternized polysulfones (PSF‐DMEA or PSF‐DMOA) with polystyrene (PS) or poly(4‐vinylpyridine) (P4VP) were prepared by the solution casting method. Pure quaternized polysulfones, in N,N‐dimethylformamide (DMF)/methanol (MeOH) and DMF/water solvent/nonsolvent mixtures, and their blends with PS and P4VP, as well, were investigated by shear viscometry and viscoelasticity, atomic force microscopy, differential scanning calorimetry, and surface properties. The results obtained revealed that the blends have good miscibility. Surface morphology is characterized by roughness and nodules formations, depending on the alkyl radical lengths, composition of the polymer mixtures, including specific electron‐donor or electron‐acceptor characteristics of polymers. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers