The development of cost-effective, efficient and stable catalysts for liquid organic hydrogen carriers (LOHC) is crucial for large-scale hydrogen storage. Herein, we introduced La species into Ni/Al2O3 via co-precipitation method, yielding La-Ni/Al2O3 catalysts. Such catalysts demonstrated exceptional performance and durability in hydrogenating various LOHC candidates. Their hydrogenation capabilities surpassed most state-of-the-art and commercial catalysts, attributing to the homogenous formation of ultrafine nanoparticles induced by La species, prevention of producing unfavorable components, optimal microstructural distributions and balanced dispersion of acid sites. DFT calculations indicated that Ni-NiO(002) interface played crucial roles in modulating the electron deficiency of surface Ni atoms. The synergistic effect of Ni0-Niδ+ shifts the d-band center of Ni closer to the Fermi level, enhancing the catalyst’s adsorption capacity of intermediates and achieving higher activity toward activation of benzene and pyrrole ring, therefore leading to rapid and deep LOHC hydrogenation. The resultant catalysts exhibited great potentials for industrial applications.