By using bathophenanthroline (BPhen) as an exciton blocking layer (EBL) at the organic/cathode contact of a standard copper phthalocyanine/C60 organic photovoltaic (OPV) device, power conversion efficiency was substantially increased from 0.86% to 2.64%. The BPhen-based devices showed a 45% increase in power conversion efficiency over that of an equivalent device with an EBL of bathocuproine. The performance improvement was analyzed in terms of the electron energy levels, optical transparencies and electron mobilities of the two EBLs. Based on these results, the roles of and requirements for an effective EBL were discussed. Combining the use of BPhen and a WO3 anodic buffer layer further increased the power conversion efficiency of the OPV device to 3.33%.