Developing efficient Ni-based catalysts and understanding the mechanism of tar removal are crucial for upgrading biomass gasification technology. Literature has identified the superior performance of Ni-based catalysts in reforming tar model compounds like toluene under a steam atmosphere. In this work, we have synthesized La1-xCexNiO3 catalysts and examined their activity with benchmark A2BO4-type perovskites in dry reforming of toluene (DRT). Catalytic experiments revealed that La0.25Ce0.75NiO3 catalysts exhibited superior activity and stability regarding toluene conversion (85.4%) compared to La0.5Ce1.5NiO4. The structural study, conducted through various techniques, highlighted the easier reducibility of Ni from the ABO3 perovskite lattice, leaving higher oxygen vacancies, and higher basicity for reactant adsorption in DRT. Besides, in-situ DRIFTS experiments confirmed the *CHO-participated pathway of syngas generation from DRT. The findings suggested potential pathways for designing catalysts to support biomass gasification while contributing to global carbon reduction.