Anodically polymerized films of nickel salen formed on glassy carbon, optically transparent tin oxide, and platinum electrodes in acetonitrile containing tetramethylammonium tetrafluoroborate have been examined by means of cyclic voltammetry, thin-layer voltammetry, spectroelectrochemistry, and scanning electron microscopy, With the aid of thin-layer voltammetry, it has been confirmed that the global oxidative polymerization of nickel(II) salen involves three electrons per monomer, Polymerization proceeds through two distinct phases, the formation of which depend on the potential. Once the polymer film has been formed, the anodic process consists of the reversible one-electron nickel(III)/nickel(II) redox couple, Cyclic voltammetry along with spectroelectrochemistry has been employed to probe the roles of the nickel(III)/nickel(II) and nickel(II)/nickel(I) redox couples in the electrochemical response of the polymer film as well as the interconversion of the different oxidation states of nickel.