We report the preparation of a new class of copolymer films that consist of polymethylene (PM) with a low percentage (similar to1-4%) of randomly distributed ethyl ester side groups, consistent with poly(methylene-co-ethyl acetate). The films are prepared through a surface-catalyzed polymerization on gold surfaces upon exposure to a dilute solution of diazomethane (DM) and ethyl diazoacetate (EDA) in ether at 0 degreesC. While EDA alone does not polymerize at gold surfaces but DM does decompose on gold to grow PM films, the combined presence of EDA and DM results in dramatic enhancements in film growth and promotes an alternative mechanism for propagation as compared with that for the PM homopolymerization. The rate of copolymer film growth is constant over a similar to24 h period, consistent with a controlled polymerization in which chain terminations are minimized. Carefully controlled experiments indicate that chain propagation does not occur at the outer film-solvent interface, but more likely, at the film-metal interface, suggesting a catalyzed insertion mechanism that extends the chain and pushes the outer chain termini further away from the metal-polymer interface. The results also suggest that adsorbed intermediates of EDA function as co-catalysts to promote the propagation reaction. Of particular importance for materials modification is that the ester side chains of these copolymer films can be hydrolyzed to carboxylate groups that exhibit pH-dependent wettability.