In the present paper, 1,5-bis[N-(1-naphthyl)-N-phenyl] naphthalene diamine (NPN) with high purity was synthesized by liquid-phase Ullmann reaction, and high quality film of NPN was formed on cleaned glass substrates by vacuum evaporation. Photoluminescence properties were studied by solvent effects on UV-Vis absorption spectra and fluorescence spectra. In addition the structure of energy band of NPN was studied by cyclic voltammetry, UV-Vis absorption spectra, and fluorescence spectra. The results indicate that the fluorescence emitting is attributed to the charge transfer transition from nitrogen to aromatic ring. The molecules of NPN in its film form "J-aggregate". The HOMO energy and optical gap of NPN are -5.74 and 2.79 eV respectively. NPN film could emit intense blue fluorescence with a peak wavelength at 448.6 nm and a bandwidth of 72.6 nm under UV-Vis excitation at 365 nm.