Nickel–iron/magnesium/aluminum bimetallic catalysts were prepared by the calcination and reduction of nickel–magnesium–iron–aluminum hydrotalcite-like compounds. Characterization suggests that, at iron/nickel≤0.5, both nickel and iron species are homogeneously distributed in the hydrotalcite precursor and incorporated into the Mg(Ni, Fe, Al)O periclase after calcination, giving rise to uniform nickel–iron alloy nanoparticles after reduction. Ni–Fe/Mg/Al (Fe/Ni=0.25) exhibits the best catalytic performance for the steam reforming of tar derived from the pyrolysis of biomass. It is suggested that the uniform nickel–iron alloy nanoparticles and the synergy between nickel and iron are responsible for the high catalytic performance. Moreover, the Ni–Fe/Mg/Al catalyst exhibits much better regenerability toward oxidation–reduction treatment for the removal of deposited coke than that of conventional Ni–Fe/α-Al2O3. This property can be attributed to the better regeneration of Ni–Fe alloy nanoparticles through the formation and reduction of Mg(Ni, Fe, Al)O.