The effect of Fe addition on catalytic activity and stability of LaNi x Fe 1−x O 3 perovskite catalyst was investigated for hydrogen production via steam reforming of tar using toluene as a model compound. The addition of Fe to LaNiO 3 catalyst at the optimum amount enhanced the catalytic performance in steam reforming of toluene. LaNi 0.8 Fe 0.2 O 3 catalyst shows the best performance in terms of catalytic activity and stability for 8 h of reaction time. The catalyst characterization indicates the presence of Ni-rich Ni–Fe smaller bimetallic particles, strong metal support interaction, and lower carbon deposition rate on LaNi 0.8 Fe 0.2 O 3 catalyst. The synergy between Ni and Fe atoms on the small Ni–Fe bimetallic particles is crucial for high activity of the LaNi 0.8 Fe 0.2 O 3 catalyst. In addition, the strong interaction between metal and support on the LaNi 0.8 Fe 0.2 O 3 catalyst can prevent metal sintering, thus, achieving high catalytic stability.