Perovskite-type oxide LaFeO3 powder was prepared using a stearic acid combustion method. Its phase structure, electrochemical properties and hydrogen storage mechanism as negative electrodes for nickel/metal hydride (Ni/MH) batteries have been investigated systematically. The results of X-ray diffraction (XRD) analysis show that both the calcined powder and the charged/discharged samples after 10 cycles have orthorhombic structures. The discharge capacity, whose maximum value appeared at the first cycle, is 530.3mAhg−1 at 333K and increases with an increase in temperature. The discharge capacity decreases distinctly during the first three cycles and then stays steady at about 80mAhg−1, 160mAhg−1 and 350mAhg−1 at 298K, 313K and 333K, respectively. The hydrogen storage mechanism is studied by XRD, X-ray photoelectron spectroscopy (XPS) and mass spectrometry (MS), coupled with pressure–composition–temperature (PCT) methods. Hydrogen atoms may be intercalating into the oxide lattice and forming a homogeneous solid solution during the charging process.