The complex formation between vinyl ether of poly(ethylene glycol-co-vinyl butyl ether) with poly(acrylic acid) has been considered in aqueous and isopropanol solutions. The effect of copolymer composition on the complex formation process was clarified. It has been shown that the incorporation of hydrophobic fragments into macromolecules enhances the hydrophobic stabilization of polycomplexes in aqueous solutions. In organic media this effect disappears. The stability of polycomplexes formed both in aqueous and in organic solutions in respect to the addition of dimethylformamide has been studied.