The electrooxidation of 8-(3-acetylimino-6-methyl 2,4-dioxopyran)-1-aminonaphthaline (AMDAN) in aqueous and non aqueous media led to the formation of polymeric films, poly (AMDAN). The monomer, undergo anodic oxidation through the formation of a monocation radical irrespective of the nature of the medium. In aqueous medium, the monocation radical undergoes, through its resonance structures, dimerisation involving tail-to-tail, head-to-tail and even head-to-head coupling. The products formed, being more easily oxidisable than the parent substance, undergo further oxidation at the same potential so that the overall oxidation involves a one-step (i.e., a single wave), two-electron process. In non-aqueous medium, the monocation radical does not undergo dimerisation through coupling reactions. Retaining its identity, monomer oxidise in two steps involving one electron in each step. The fact that the cathodic peaks corresponding to these anodic peaks are rarely observed indicates fast consumption of the electrogenerated monocation radicals and dications by follow-up chemical reactions to produce polymeric products (poly AMDAN). The electrochemical behavior of the formed polymer films was investigated in both non aqueous and aqueous media. The films prepared in non aqueous medium were found to be more electroactive than that the films prepared in aqueous medium. This is confirmed with the results in litreature which illustrate that the film prepared in aqueous solution hold water in its structure via hydrogen bonding, which causes decomposition reactions.