As catalytic reaction usually occur on the surface of a catalyst, regulating the catalyst morphology may largely affect the photocatalytic properties. A series of Zn0.5Cd0.5S catalysts with different shapes, namely nanoparticles, nanorods, microsheets, and microspheres, were prepared through hydrothermal/solvothermal reaction by controlling the sulfur source, solvent, and the adding sequence of the raw material. Moreover, their photocatalytic H-2 production in different solvents, including H2O, formic acid, lactic acid, and Na2S/Na2SO3, were investigated. The addition of the sacrificial agents could inhibit the photocorrosion caused by the strong oxidation of holes (h(+)), increasing the amount of photogenerated electrons (e(-)) to produce H-2. Zn0.5Cd0.5S nanoparticles and nanosheets displayed much higher activity than other samples due to the effective separation of photogenerated charge carriers (PCCs), large specific surface area, and negative position of the conduction band.