A series of photovoltaic heterojunctions of the typen‐Zn0.1Cd0.9S/p‐CdTe have been prepared by spray pyrolysis of ZnCdS films on single‐crystal CdTe with variation of the CdTe substrate temperature and of the postdeposition heat‐treatment temperature in hydrogen. Open‐circuit voltages as high as 0.82 V are observed compared to maximum values of 0.74 V observed forn‐CdS/p‐CdTe junctions also prepared by spray pyrolysis. Cell efficiencies are in the 6–8&percent; range without correction for reflection losses.