A series of pure and 50 % substituted Fe-containing (LaFeO3, LaFe0.5Ni0.5O3 and LaFe0.5Co0.5O3) and Co/Ni-containing (LaCoO3, LaNiO3, and LaCo0.5Ni0.5O3) perovskites were used as precursors to synthesize metallic reduced catalysts to be tested for the liquid hydrogenation of furfural. The catalytic reaction was carried out in a batch reactor at 200 degrees C and 3.0 MPa of H-2 pressure. The calcined perovskites and reduced catalysts were characterized by X-ray diffraction (XRD), N-2 physisorption at 77 K, temperature programmed reduction (H-2-TPR), temperature programmed CO2 and NH3 desorption (CO2-TPD and NH3-TPD), Atomic Absorption Spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS) techniques. The LaCo0.5Ni0.5O3 reduced catalyst display the highest activity in furfural conversion, which was attributed to a cooperative effect between highly dispersed nickel and cobalt metal nanoparticles after reduction process. The effect of the nature of B-cation have a high impact on the products selectivity in the hydrogenation of furfural, suggesting that enriched-Ni metal surface was selectivity to tetrahydrofurfuryl alcohol, meanwhile enriched-Co metal surface was selective to furfuryl alcohol formation, which was also supported with adsorption mode of furfural over the active sites obtained by quantum calculation.