Polyurethane and polyurethane cationomers were synthesized using 2,3-dihydroxypyridine and 2,3-dihydroxypyridine hydrochloride as chain extenders. Poly(butyl methacrylate-co-methacrylic acid) was synthesized by free radical solution polymerization and was converted into its sodium salt. The polyurethane cationomer and the acrylic anionomer were blended in different proportions in N,N-dimethylformamide. Simple blends without ionic groups were also prepared. Miscibility enhancement in these systems was studied by means of differential scanning calorimetry and scanning electron microscopy.