Transition metal polymers containing alkane-linked bi- and ter-pyridine ligands have been prepared and studied as thin films deposited on electrode surfaces. The cobalt and iron containing polymers exhibit electrochemical behavior similar to that of the corresponding monomers and to polymers formed by reductive polymerization of vinyl-containing monomers (in cases where such polymers exist). Despite these similarities, in several instances the present polymers exhibit distinctly different behavior with regard to their ability to catalyze the reduction of CO2 and O-2, when compared to soluble monomers and other supposedly similar polymers. Consideration is given to potential structural differences that may give rise to differences in catalytic activity.