Organic/silicon hybrid structures have been extensively studied for the application of solar cells due to their high photoelectric conversion efficiency and simple fabrication process. However, studies of lateral photovoltaic effects (LPEs) in the devices are still scarce. Herein, the Si/SiO2/PEDOT:PSS devices were prepared by spin-coating, and showing the lateral photovoltage (LPV) sensitivity of 14.0 mV/mm at room temperature, which is higher than the control samples of Si/SiO2 (0.1 mV/mm) and Si/PEDOT:PSS (9.0 mV/mm) structures. With the decrease in temperature, the lateral photovoltage increases initially, and reaches a peak at around 210 K, then drops accordingly. The enhancement of LPE can be mainly ascribed to the formation of the p-n junction and the native oxide layer at the organic/inorganic interface.