A facile synthetic pathway using poly(4-vinylpyridine) as a polypyridyl platform is reported for the formation of a metallopolymer. Electrochemical studies indicate that the metallopolymer acts as an efficient H-2 evolution catalyst similar to cobalt polypyridyl complexes. It is also observed that the metallopolymer is transformed to cobalt particles when a cathodic potential is applied in the presence of an acid. Electrochemical measurements indicate that an FTO electrode coated with these cobalt particles also acts as an efficient hydrogen evolution catalyst. Approximately 80 A mu moles of H-2 gas can be collected during 2 h of electrolysis at - 1.5 V (vs. Fc(+/0)) in the presence of 60 mM of acetic acid. A comprehensive study of the electrochemical and electrocatalytic behavior of cobalt-poly(4-vinylpyridine) is discussed in detail.