Photovoltage properties of multilayer Langmuir-Blodgett (LB) films of corbathiene (∼100 nm thick) on the n-Si substrate with semitransparent top gold electrode have been investigated. Measurements of photovoltage dependence on wavelength and intensity of exciting light have been performed. The photovoltage values attaining 0.4 V are well reproducible when subjected to illumination of intensity up to 10¹⁴ photons cm^-2 s^-1 in the wavelength range 300-900 nm. The results are related to the major role of the film/substrate interface and to the films optical absorption features.