Noble metal-based heterogeneous catalysts usually suffered from limited strategies for modifying their selectivity as compared with the homogeneous counterparts. Herein, we reported the electrostatically mediated selectivity of Pd nanocatalyst of usual supported Pd nanoparticles for total hydrogenation of furfural by enhancing the interfacial electric field using visible light and a rectifying contact with semiconductive supports to promote preferred adsorption of C=Ogroups of furfural to the Pd side. This concept-new approach showed the potential to replace traditional organic ligands with light. The Pd nanoparticles deposited on a semiconductor support, optimized to be g-C3N4 (Pd/CN) in this work, exhibits outstanding selectivity (>= 97%) to tetrahydrofurfuryl alcohol, far surpassing the selectivity of reported single-phase Pd nanocatalysts.