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[Display omitted] Photorefining of biomass is increasingly recognized as a pivotal technology for the simultaneous production of hydrogen and value-added chemicals. The intrinsic recalcitrance of lignocellulosic biomass puts high demands on the rational design of bifunctional photocatalyst. Herein, Ni 2 P/CdS with a strong interfacial effect in this work was designed to overcome lignocellulosic biomass photorefining. The strong interfacial effect between Ni 2 P and CdS not only improved the light absorbance, but also optimized the spatial redistribution of photogenerated electrons and holes. Therefore, Ni 2 P/CdS exhibited an unprecedented H 2 evolution activity (ca. 199.7 mmol·h−1·g−1) in the presence of lactic acid as the traditional sacrificial agent. Considerable H 2 generation was also achieved in the presence of lignin (ca. 322.8 μmol·h−1·g−1), cellulose (ca. 534.3 μmol·h−1·g−1) and hemicellulose (ca. 382.2 μmol·h−1·g−1) as the electron donor respectively. Theoretical calculation results indicated that establishing the interfacial effect between Ni 2 P and CdS optimized their work functions. This optimization fosters improved the redistribution between electrons and holes, as a result, photocatalytic hydrogen production from biomass solution was greatly enhanced. Significantly, Ni 2 P/CdS showed dual functionalities to produce H 2 and value-added compounds from raw biomass directly. This present work demonstrates the potential of raw biomass photorefining through astutely designing photocatalysts. [ABSTRACT FROM AUTHOR]