The water-soluble composites with fullerene content up to 5 wt% based on poly-(N-vinylpyrrolydone) (PVP) were obtained. The higher fullerene content is achieved by means of introducing tetraphenylporphyrine (TPP) and KBr into composites. The synthesis includes the formation of C₆₀-TPP complex and its further interaction with polymer. The formation of C₆₀-TPP complex was confirmed by ¹³C NMR, SANS, and translational diffusion. The hydrodynamic and electrooptical studies of C₆₀-TPP-PVP complexes indicate the higher symmetry of the polymer coil in the complex as compared to PVP. The C₆₀-PVP-KBr composites were also obtained by the solid state interaction under vacuum, KBr promoting the destruction of fullerene aggregates.