The new type doping method, VUV-induced doping, has been applied to copper phthalocyanine (CuPc) thin film. The highest occupied molecular orbital (HOMO) peak in the ultraviolet photoelectron spectrum of CuPc film was gradually shifted toward high binding energy side upon the irradiation of He I alpha radiation. Furthermore, the radiation induced gap states were observed up to the Fermi level. The shift of the HOMO peak in the low-dose region depends in a semi-logarithmic fashion on the irradiation time, indicating that the intentional n-type doping of CuPc film can be realized by VUV irradiation.