Hybrid metal ion and polyvinyl alcohol (PVA) was prepared to obtain La 1−x Ce x NiO 3 (x = 0, 0.2, and 0.4) perovskite-type catalyst powder by sol-gel method. Metal ion to PVA monomer molar ratio was assigned at 1:1. The metal ion formed into complex precursors with alkoxide to improve the elemental dispersion and prevent agglomeration of obtained catalyst which is strongly related to activity and stability on syngas generation. As-prepared catalysts were calcined at 800 °C and characterized. X-ray diffraction pattern confirmed high crystalline of LaNiO 3 perovskite structure and additional CeO 2 phase was founded when La was partial substituted by Ce. The crystal size and particle size of La 1−x Ce x NiO 3 tended to decrease with higher Ce content. SEM and EDS results confirmed good elemental dispersion with homogeneous structure and low agglomeration. Particle size and surface area were in the range of 13.85–16.70 μm and 2.40–5.87 m 2 /g, respectively. Temperature programmed reduction (TPR) of prepared catalyst show highest H 2 consumption at 390 °C and 700 °C which were attributed to the partial reduction of Ni 3+ to Ni 2+ and Ni 2+ to Ni 0 , respectively. Activity of catalyst on steam reforming of tar was investigated using toluene as model compound in a fixed bed quartz reactor at 500–800 °C with steam/carbon molar ratio of 2:1. Carbon and hydrogen conversion were interpreted in term of CO 2 , CO, H 2 , and C x H y as CH 4 . The effect of operating temperature appeared to improve favorable fuel gas species formation in terms of selectivity and quantity. Addition of La 0.6 Ce 0.4 NiO 3 catalyst promoted conversion of toluene to CO and H 2 at the highest yield of 57.26% and 76.62% at 800 °C, respectively. Moreover, catalysts showed favorable stability because no deactivation was observed during the 180 min of test. LHV of syngas obtained can be used for power production without need for auxiliary fuel.