<p>The development of highly efficient and selective metal-acid bifunctional catalysts with excellent synergy is essential for obtaining target products and reducing carbon loss in biomass upgrades. Here, a strategy of surface Brønsted acid local enrichment induced by hydrogen spillover is proposed to optimize the metal-acid synergy. The Ni/10TiO₂/ZSM-22 catalyst, which features Ni nanoparticles and ZSM-22 separated by a sub-nanometric TiO₂ porous film, was prepared using atomic layer deposition to improve the palmitic acid hydrodeoxygenation performance. The TiO₂ film facilitates hydrogen spillover, improving the hydrogenation activity of metal sites. Approximately 75% of the original surface Brønsted acid sites (BASs) on ZSM-22 are covered by the porous TiO₂, and the surface BAS concentration of Ni/10TiO₂/ZSM-22 is increased due to the facilitated hydrogen spillover, <i>i.e.</i>, the surface BASs are enriched locally in the zone of TiO₂ pores. Thanks to the surface BAS local enrichment, the formation of byproduct pentadecane is inhibited, and the intermediate 1-hexadecanol is rapidly converted, obtaining notable hexadecane selectivity. This strategy is also effective for the Pt/10TiO₂/ZSM-22 catalyst, resulting in nearly 100% hexadecane yield (99.6%). This research provides valuable insights into designing highly efficient bifunctional catalysts for energy conversion.</p>