The photoluminescence (PL) of high quality GaN epitaxial layer grown by MOCVD was investigated for various excitation power and temperatures from 8.3 to 300K. The PL at 8.3 K and with relatively low excitation power of GaN film grown on c-plane sapphire by using MOCVD shows clearly free-exciton A, B and exciton A bound to neutral donors (D o X) at 3.502 eV, 3.509 eV, and 3.496 eV, respectively. The full width at half maximum (FWHM) and binding energy of exciton A of the high quality GaN film were evaluated as small as 3.7 meV and 27.9 ± 0.5 meV, respectively. In addition, PL and Raman scattering of GaN films grown on r-plane sapphire and (111) Si substrates by using MOCVD were examined. The residual stress effect was detected in all films.