p-CuSCN/n-ZnO rod array heterojunctions were electrodeposited with a weak basic (pH similar to 9) aqueous electrolyte solution. I-V characteristics showed the heterostructure had clear rectification, indicating good electrical contacts between ZnO rod arrays and the embedded CuSCN. The energy band model for the electrodeposition of CuSCN on ZnO rod arrays was proposed based on linear sweep voltammetric (LSV) measurements, which indicated that the electrodeposition process was the prior growth of CuSCN on bare ZnO rods according to a conduction process, followed by compact filling in the gaps of the arrays based on the thermal activation mechanism of surface states. The diode properties of the heterojunctions, revealed that although deposition was dominated by thermal activation mechanism of surface states, the electrodeposition should be performed at a lower temperature in order to reach fine filling of the gaps of ZnO rod arrays. (C) 2008 Published by Elsevier Ltd.