Electron energy-loss near edge structure (ELNES) was measured with parallel-EELS in the carbon and the nitrogen K-edges of the chlorinated Cu-phthalocyanine and poly GeO-phthalocyanine as a function of irradiation dose. The intensity of the first ELNES peak, which was attributed to the 1s --> pi* transition peak in both edges, was decreased with an increase of irradiation dose. This fact clearly shows the unoccupied pi* molecular orbitals were changed in the course of electron irradiation. This 1s --> pi* transition peak of the chlorinated Cu-Pc fades more slowly than that of the poly GeO-Pc, which can be understood by the "cage effect" of the atoms liberated from the molecules. Moreover, it was observed that the fading of the nitrogen 1s --> pi* transition peak was rapid in comparison with that of the carbon peak in the poly GeO-Pc film. This suggests that the radiation damage may be a site-dependent process in the poly GeO-Pc.