The tridentate ligand L and its complexes with transition-metal ions have been prepared and characterized. The polycondensation reactions of transition-metal complexes with different dialdehydes led to the formation of transition-metal-complex-based polyazomethines, which have been obtained by on-substrate polymerization, and their electrochemical and electrochromic performance have been investigated. The most interesting properties are exhibited by polymers of Fe(II) and Cu(II) ions obtained by the reaction of the appropriate complexes with a triphenylamine-based dialdehyde. Fe(II) polymer P1 undergoes a reversible oxidation/reduction process and a color change from orange to gray due to the oxidation of Fe(II) to Fe(III) ions concomitant with the oxidation of the triphenylamine group. Its electrochromic properties such as long-term stability, switching times, and coloration efficiencies have been investigated, providing evidence of the utility of the on-substrate polycondensation reaction in the formation of thin films of electrochromic metallopolymers.