Poly (4-hydroxybenzaldehyde) was prepared by via the oxidative polymerization process in an aqueous alkaline medium by H2O2 as an oxidant. Then, poly(phenoxy-imine)s were synthesized from the condensation reactions of poly(4-hydroxybenzaldehyde) (P-4HBA) with several amines including pyridine and pyrimidine groups. The structures and characterizations of compounds were made by virtue of FT-IR, NMR, UV-Vis spectroscopy, GPC, TG, DSC, CV, SEM and fluorescence (FL) analyses. The conductivities of poly (phenoxy-imine)s were determined with electrometer by four-point probe technique. The conductivity values of poly (phenoxy-imine)s were increased to be connect with doped factor of iodine. Moreover, the electrical conductivity of the poly (phenoxy-imine)s was also measured and defined which they had semi-conductive features. Fluorescence properties of poly (phenoxy-imine)s and P-4HBA were measured out in DMF solutions to define the optimum concentrations in order to acquire the maximal FL intensities. Average molecular weight of the polymers in number (M-n), and in weight (M-w), and polydispersity index (PDI) values of poly (phenoxy-imine)s and P-4HBA were found from GPC analysis. The M-n, M-w and PDI values of P-4HBA were found to be 9900 Da (M-n), 11,300 Da (M-w) and 1.14, respectively. The electrochemical energy gap (E'(g)) and optical band gap (E-g) values of poly (phenoxy-imine)s were determined from cyclic voltammetry (CV) and UV-Vis measurements, respectively.