A novel CdSe/NiO heteroarchitecture was designed, prepared, and used as a photocathode for hydrogen generation from water. The composite films were structurally, optically, and photoelectrochemically characterized. The deposition of CdSe on the NiO film enhanced light harvesting in the visible-light region and photoelectrochemical properties. Moreover, the CdSe/NiO photoelectrode showed superior stability both in nitrogen-saturated and air-saturated neutral environments. The CdSe/NiO photoelectrode after MoS2 modification retained the stability of the CdSe/NiO electrode and exhibited higher photocatalytic and photoelectrochemical performances than the unmodified CdSe/NiO electrode. In pH 6 buffer solution, an average hydrogen-evolution rate of 0.52 μmol h(-1) cm(-2) at -0.131 V (versus reversible hydrogen electrode, RHE) was achieved on a MoS2 /CdSe/NiO photocathode, with almost 100 % faradaic efficiency.