Most of the photocathode semiconductors that can be used for hydrogen production are difficult to prepare or get corroded in the electrolyte of an aqueous solution. Hence it is a huge challenge to develop stable photoelectrochemical (PEC) hydrogen evolution systems. Perovskite-type LaFeO₃, as a new p-type semiconductor, is used in the PEC hydrogen evolution reaction and shows excellent stability. We synthesized a high-purity LaFeO₃ nanorod array on an FTO substrate and its bandgap is 2.14 eV. Moreover, the carrier migration efficiency of a LaFeO₃ photocathode is improved by doping with Li ions, and the doping effect also causes a red-shift of the optical maximum absorption edge. As a result, the photocurrent density of the Li-doped LaFeO₃ photocathode is increased from −30 μA cm⁻² (LaFeO₃) to −50 μA cm⁻² at 0.4 V (vs. RHE). Herein, the Li-doped LaFeO₃ show great potential as a PEC photocathode for achieving an efficient, stable and inexpensive PEC hydrogen evolution reaction.