Abstract To achieve a high solar‐to‐hydrogen (STH) conversion efficiency, delicate strategies toward high photocurrent together with sufficient onset potential should be developed. Herein, an SnS semiconductor is reported as a high‐performance photocathode. Use of proper sulfur precursor having weak dipole moment allows to obtain high‐quality dense SnS nanoplates with enlarged favorable crystallographic facet, while suppressing inevitable anisotropic growth. Furthermore, the introducing Ga2O3 layer between SnS and TiO2 in SnS photocathodes efficiently improves the charge transport kinetics without charge trapping. The SnS photocathode reveals the highest photocurrent density of 28 mA cm−2 at 0 V versus the reversible hydrogen electrode. Ove...