A novel amphiphilic C(60)EDTA derivative forms a stable monolayer on water subphases containing metal cations such as Ca2+, Cd2+, CU2+, Nd3+, or EU3+. The monolayer films can be effectively transferred to ITO or normal glass substrates. XPS spectra show that the metal cations are incorporated into the Langmuir-Blodgett films, which exhibit photoinduced electric current. The resemblance of the action and absorption spectra of the modified ITO electrodes suggests that the C(60)EDTA-Mn+ films are responsible for the generation of the photocurrent. The photocurrent flow direction of these C(60)EDTA-Mn+ films (anodic) is different from that for C(60)EDTA films (cathodic). Films containing rare earth elements exhibit a relatively large photocurrent compared with that for films containing other metals. Some factors that may influence the photocurrent generation have been studied, and the mechanism of the photocurrent is proposed.