Nowadays, the study of environmentally friendly ways of producing hydrogen as a green energy source is an increasingly important challenge. One of these potential processes is the heterogeneous photocatalytic splitting of water or other hydrogen sources such as H2S or its alkaline solution. The most common catalysts used for H2production from Na2S solution are the CdS-ZnS type catalysts, whose efficiency can be further enhanced by Ni-modification. In this work, the surface of Cd0.5Zn0.5S composite was modified with Ni(II) compound for photocatalytic H2generation. Besides two conventional methods, impregnation was also applied, which is a simple but unconventional modification technique for the CdS-type catalysts. Among the catalysts modified with 1% Ni(II), the impregnation method resulted in the highest activity, for which a quantum efficiency of 15.8% was achieved by using a 415 nm LED and Na2S-Na2SO3sacrificial solution. This corresponded to an outstanding rate of 170 mmol H2/h/g under the given experimental conditions. The catalysts were characterized by DRS, XRD, TEM, STEM-EDS, and XPS analyses, which confirmed that Ni(II) is mainly present as Ni(OH)2on the surface of the CdS-ZnS composite. The observations from the illumination experiments indicated that Ni(OH)2was oxidized during the reaction, and that it therefore played a hole-trapping role.