The surface potential built across vacuum deposited phthalocyanine (Pc) films on aluminum electrode was investigated by means of electro-modulation spectroscopy. The sandwich-type cells with thin air gap, which becomes a good insulator were used in order to avoid the influence of charge injection. The existence of the surface potential at the metal/organic-material interface induced 1f referenced electro-reflectance (ER) signals. As a result, the surface potential built across vacuum deposited Pc films on aluminum electrode was estimated to be 1.25 V.