Copper-based quaternary sulfide nanomaterials, especially for Cu-Zn-In-S (CZIS) and Cu-Zn-Ga-S (CZGS), which consist of non-toxic elements are attractive candidate for solar photocatalytic hydrogen production due to their tunable bandgap, good chemical and thermal stability, environmental benignity, and facile synthesis from abundant and inexpensive starting materials. Unfortunately, the low electric conductivity, rapid recombination rate of photogenerated electrons and holes as well as the less accessible surface-active sites have greatly limited their photocatalytic performance.