Schiff bases polymers were synthesized from 2-hydroxybenzaldehyde (2-HBA) vin oxidative polymerization method in an aqueous alkaline medium in the presence of NaOCI as an oxidant. Then, these polymeric Schiff bases were prepared from the polyaldehyde by grafting each of them with different amines containing pyridine and pyrimidine groups. The structures of polymers were confirmed by FT-IR, H-1 NMR, C-13 NMR, and UV-Vis measurements. The polymers were characterized by GPC and SEM analyses. Furthermore, their optical properties were determined by UV-Vis and fluorescence spectroscopy, their electrochemical properties by cyclic voltammetry (CV) analysis and solid state conductivity measurements by the four-point probe technique, their thermal behavior by TG, DTA, and DSC measurements. The electrical conductivity of the polymers was also measured and found that they are semiconductive. The number average molecular weight ((M) over bar (u)), the weight average molecular weight ((M) over bar (w)), and dispersity (D) values of the polymers were found from GPC analysis and were equal 5900, 5450 and 1.08, respectively, for poly(2-hydroxybenzaldehyde) (P-2HBA) polymer. Electrochemical energy gap (E-s) was found by CV, whereas optical band gap (E-s,) was determined by UV-Vis measurements.