In this study, novel types of poly(azomethine-naphthalene)s were synthesized containing naphthalene unit along the main chain in two steps. In the first step, symmetrical Schiff base diols that contain naphthalene unit in center and in the second step, poly(azomethine-naphthalene)s expanding with C-C coupling were obtained by elimination and oxidative polycondensation reactions, respectively. These purely synthesized compounds were characterized by UV-Vis, FT-IR, 1H-NMR and 13C-NMR analyses, and also their electrochemical, thermal, photonic and surface properties were illuminated by cyclic voltammetry (CV), thermogravimetric analysis, differential thermal analysis, differential scanning calorimetry, photoluminescence and scanning electron microscopy analysis techniques. According to TG analysis, char % amounts of P-2HBAN, P-2HNAN, P-4HBAN and P-3H4MBAN were found to be 9.3, 18.0, 66.6 and 47.1, respectively, at 1000 degrees C. Also, these compounds have glass transition temperature (Tg) higher than 127 degrees C and onset temperature higher than 153 degrees C. For this reason, they are useful for the production of thermal-resistant materials. In addition, electrochemical and fluorescence properties of all the compounds were examined by CV and fluorescence spectrophotometer measurements, respectively.