Copper thiocyanate (CuSCN) has proven to be a low-cost, efficient hole-transporting material for the emerging organicinorganic perovskite solar cells. Herein, we report that CuSCN can also be applied to CdTe thin-film solar cells to achieve high open-circuit voltages (V OC s). By optimizing the thickness of the thermally evaporated CuSCN films, CdTe cells fabricated by close space sublimation in the superstrate configuration have achieved V OC s as high as 872 mV, which is about 20-25 mV higher than the highest V OC for the reference cells using the standard Cu/Au back contacts. CuSCN is a wide bandgap p-type conductor with a conduction band higher than that of CdTe, leading to a conduction band offset that reflects electrons in CdTe, partially explaining the improved V OC s. However, due to the low conductivity of CuSCN, CdTe cells using CuSCN/Au back contacts exhibited slightly lower fill factors than the cells using Cu/Au back contacts. With optimized CdS:O window layers, the power conversion efficiency of the best CdTe cell, using CuSCN/Au back contact, is 14.7%: slightly lower than that of the best cell (15.2%) using Cu/Au back contact.