- Controlling charge transfer at indium-doped tin oxide (ITO)/conductive polymer junctions is of special importance for organic photovoltaic (OPV) devices and organic light emitting diodes (OLEDs), where ITO is often the transparent electrode of choice. Light induced conductance enhancement, i.e., photoconductance, can allow such control. ITO/ conductive polymer junctions are shown herein to exhibit photoconductance under UV illumination mostly due to photo-induced decrease of an electron barrier at the ITO-polymer interface by discharging of ITO extrinsic surface states, related to the adsorption of oxygen species. Furthermore, we show that ITO surface modification by photo-active porphyrin adsorption can sensitize the ITO/conductive polymer junctions extending the photoconductance to the visible range, to which ITO is transparent. This process is ascribed mostly to discharging of ITO adsorbate states by recombination with photo-generated holes in the photo-excited molecules. Such sensitization is highly relevant for organic optoelectronic devices utilizing ITO interfaced with photoactive organic species and operating in the visible range, such as OPV and OLED devices, and might be applicable also to other UV-photoconductive metal oxide electrodes.