Poly(vinyl alcohol) (PVA) was reacted with strong base NaH to yield pendant oxy anions, followed with nucleophilic addition to C60. The resulted PVA(C60-Na+)n products were then converted to PVA(C60H)n by stirring with a strong acid cation exchanger of H+-form. Extraction of the C60-containing PVAs by toluene, which is a good solvent for C60, exhibits no color transfer to the toluene phase. The C60-containing PVAs were identified by the characteristic IR and UV-Vis absorptions of C60. The electrochemical behaviors in solution or in film state were investigated by cyclic voltammetric methods. The cyclic voltammogram of 4a shows a reduction peak at −2.30 V which should be due to the bonded C60 chromophores. In the film state, obtained by coating C60-containing PVA solution on graphite electrode, PVA(C60-Na+)n is much easily reduced and oxidized than PVA(C60H)n. Furthermore, the difference in this reduction and oxidation feasibility is enhanced with increasing C60 content. However, coating with PVA(C60H)n or PVA(C60-Na+)n reduces the redox ability of the graphite electrode.