The work function (WF) of indium-tin-oxide (ITO) substrates plays an important role on the inverted organic photovoltaic device performance. And electrode engineering has been a useful method to facilitate carrier extraction or charge collection to enhance organic photovoltaic (OPV) performance. By using self-assembly technique, we have deposited poly(dimethyl diallylammonium chloride) (PDDA) layers onto ITO coated glass substrates. The results indicate that the surface WF of ITO is reduced by about 0.3 eV after PDDA modification, which is attributed to the modulation in electron affinity. In addition, the surface roughness of ITO substrate became smaller after PDDA modification. These modified ITO substrates can be applied to fabricate inverted OPVs, in which ITO works as the cathode to collect electrons. As a result, the photovoltaic performance of inverted OPV is substantially improved, mainly reflecting on the increase of short circuit current density.