Contents A growth-temperature-mediated two-step chemical vapor deposition strategy is designed to synthesize MoS2/WS2 and WS2/MoS2 stacks on Au foils. Predominantly A-A stacked MoS2/WS2 and A-B stacked WS2/MoS2 are selectively achieved and confirmed. Relative enhancements or reductions in photocatalytic activities of MoS2/WS2 or WS2/MoS2 are observed under illumination, because the type-II band alignment enables directional electron flow from electrode to active site.