Herein, we report the synthesis of quaternary chalcopyrite sulfide semiconductors Cu2MSnS4 (M = Zn, Ni, Co, Mn, Fe) by a hydrothermal process. The formation of kesterite structure was confirmed by XRD. XPS analysis confirmed the composition of Cu-(Zn, Ni, Co, Mn, Fe)-Sn-S. Morphologies of the hierarchical structures were characterized. Hall measurements revealed that the Zn was replaced with Ni which exhibited higher carrier density and lower resistivity. Cyclic voltammetry measurements showed peak-to-peak separation (E-pp) value of Cu2NiSnS4 about 268 mV, which was smaller than that of Cu2ZnSnS4, and a higher cathodic current density (I-c) of 0.000334 mA cm(-2) compared to those of Pt. This indicated that the electrocatalytic activity of Cu2NiSnS4 was better for the I-/I3- redox reaction, with a long-term stability for 250 cycles.