The facile hydrothermal synthesis of Zn 10 In 16 S 34 atomically thin nanosheet arrays on fluorine-doped tin oxide glass (FTO) substrates is presented. Through controlling heat treatment in air,O -doping and Zn, Sv acancies were simultaneously introduced in Zn 10 In 16 S 34 nanosheets with adjusted phase,m orphology,c hemical compositions,a nd energy level distribution. The surface defect states are passivated by depositing ultrathin Al 2 O 3 film by atomic layer deposition technology.T he performance of Zn 10 In 16 S 34 photoanodes is largely improved, with 4.7 times higher current density and reduced onset potential. The experimental results and density functional theory calculations indicate that the enhancement is attributed to the fast photoexcited electron-hole pair separation, decreased surface transfer impedance,p rolonged carrier lifetime,a nd reduced overpotential of oxygen evolution reaction.