Polyazomethines containing silane and phosphazene groups were synthesized via elimination reactions of dihydroxy compounds containing imine bonding with phosphazane and silane dichloride. The structures of monomers and polymers containing phosphazane and silane groups were supported by H-1-NMR, C-13-NMR, FT-IR and UV-Vis techniques. Electrochemical properties of the prepared Schiff bases and polymers were given by cyclic voltammetric (CV) analysis. Thermal properties of synthesized monomers and polymers were determined by TG-DTA and TG-DTA, DMA and DSC techniques, respectively. Molecular mass distributions of polymers are determined with gel permeation chromatography (GPC) measurement. Morphologic images of polymers containing heteroatom (silane/phosphazene) and azomethine linkage in the main chain were investigated by SEM techniques. The electrochemical band gap values of SB-1, SB-2, P-1, P-2 and P-3 compounds were found as 3.09, 3.30, 2.63, 3.07 and 3.04 eV, respectively.