ZnO nanorod array and dense grain film on ITO glass was grown by one-step electrodeposition at 85 and 55 °C, respectively. Hybrid solar cells composed of polymer blends and the electrodeposited ZnO were produced. We demonstrated the correlation between the location of the dominant defects in the electrodeposited ZnO and the performance of the corresponding hybrid solar cells by correlating the morphologies of the hybrid solar cells, the shift phenomena of the photoluminescent visible emission bands of the electrodeposited ZnO, and the photovoltaic behaviors of the solar cells. The defects located at the root of the ZnO rods can cause serious current leakage for the hybrid solar cells. The elimination of the current leakage can be achieved by cutting off the direct contact between the polymer blend and the root of the nanorods by either growing denser rods or annealing treatment.