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 (Epp) value of Cu2NiSnS4 about 268 mV, which was smaller than that of Cu2ZnSnS4, and a higher cathodic current density (Ic) 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. [ABSTRACT FROM AUTHOR]