Abstract Interpolymer complexes of a slightly basic polymer, poly( N-vinylimidazole) (PVIm) with a strongly acidic polymer, poly(acrylic acid) (PAA) have been prepared by mixing aqueous solutions of the respective components. Spectroscopy and thermal methods were used to reveal interaction between VIm and AA moieties. FT-IR analysis showed that the nitrogen atoms at 3rd position of imidazole ring are involved in strong H-bonding with acid groups of PAA leading to a uniform and fully miscible complex structure. As the quantity of PAA increases the thermal stability of complex increases based on TG results. In the DSC analyses, the single T g for all IPC samples showed that IPCs have good or definite miscibility over the whole range of composition as a result of H-bond formation between acrylic acid and imidazole units.