Water-soluble methanofullerene and fulleropyrrolidine derivatives were synthesized by the reactions of methanofullerenes (MFs) and fulleropyrrolidines (FPs) with poly(N-vinylpyrrolidone) (PVP) bearing one terminal amino group. The products contain MF or FP covalently bound to the polymer, corresponding polymeric complexes, and unreacted PVP. Large aggregates of the polymeric MF and FP derivatives are found in aqueous solutions. The electrooptical properties of the products differ considerably from those of the initial polymer. The phosphorus-containing MF and FP derivatives are capable of cleaving the molecule of plasmid DNA.