Cu2O/ZnO p-n heterojunction solar cells were fabricated by rf sputtering deposition of n-ZnO layer, followed by electrodeposition of p-Cu2O layer. The different electrodeposition potentials were applied to deposit Cu2O on ZnO. The particle size, crystal faces, crystallinity of Cu2O is important factor which determine the p-n junction interface and consequently their effect on the performance of the heterojunction solar cell. It is observed that at -0.6V, p-Cu2O film generates fewer surface states in the interband region due to the termination of [110] resulting in higher efficiency (0.24%) with maximum particle size (53 nm). The bandgap of Cu2O at this potential is found to be 2.17 eV. Furthermore, annealing of ZnO film was performed to get rid of deteriorating one and two dimensional defects, which always reduce the performance of solar cell significantly. We found that the solar cell performance efficiency is nearly doubled by increasing the annealing temperature of ZnO thin films due to increasing electrical conductance and electron mobility. Doping studies and fine tuning of the junction morphology will be necessary to further improve the performance of Cu2O/ZnO heterojunction solar cells. (C) 2011 Elsevier Ltd. All rights reserved.