The electrochemical behaviors of a novel class C-60 covalently linked PPV derivatives (i.e., PPV-1-C-60 and PPV-2-C-60) in thin solid films as well as in solutions are reported. The first cathodic peak potentials of PPV-1-C-60 and PPV-2-C-60 have positive shifts by 30 and 50 mV, respectively, compared to pristine C-60 in formal cyclic voltammetry (CV). Simultaneous CV and piezoelectric microgravimetry of the drop-coated thin solid films of PPV-1-C-60 and PPV-2-C-60 in acetonitrile solutions of TBA(+) counteractions are strongly influenced by the structure of the polymer-C,,, including the length of the chain macromolecule and the steric hindrance effect. In addition, the atomic force microscopy (AFM) images of PPV-1-C-60 and PPV-2-C-60 films deposited on Au/quartz electrode both exhibit even distribution.