Processes of electrooxidation of complex palladium compounds with the Schiff bases containing various substituents are considered on the basis of spectroscopic and electrochemical data. The processes lead to the formation of electroconducting polymer complexes at the electrode surface. A general mechanism, proposed for the electrooxidation of these compounds, accounts for the effect of the metallic center, ligand, and solvent nature. The satisfactory agreement between spectroscopic and electrochemical studies and a computer-aided modeling testifies that the conclusions are reliable. The results may be useful for controlled syntheses of new conducting polymer compounds and their application in catalytic and optoelectronic systems.