The photosensitive hybrid structures poly-3,4-ethylenedioxythiophene (PEDOT)- porous silicon (PS)-n-Si are fabricated. Current-voltage characteristics of the obtained structures are investigated. It is shown that PS surface modification by PEDOT conjugated polymer gives rise to the appearance of a pronounced rectifying effect on the current-voltage characteristics. Spectral characteristics of photoresponse in the 450-1100nm wavelength range, its temperature dependence in the 125-325K range, and energy characteristics of the hybrid photovoltaic structures are studied. We propose possible mechanisms of the photoelectric processes in the hybrid structures PEDOT-PS-n-Si.