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To span the inherent application limitation of state-of-the-art catalysts for the chemical transformation of biomass derivatives, here, we formulate a series of Pr–Ni–P catalysts for the hydrogenation transformation of biomass-derived levulinic-acid, furfural and maleic anhydride. With comprehensive characterizations, Pr–Ni–P samples are verified as (PrPO4)m/Ni2P nanocomposites with a molar ratio (m) in the range of 0.24–11.0. In comparison with the poor catalytic performance of Ni2P, a ten-fold enhancement in TOF up to 0.45 s−1 and at least five-time promotion on the yield of objective products up to 91–98% are achieved by introducing proper amounts of PrPO4 to form reusable (PrPO4)m/Ni2P nanocomposites. Surface chemistry and kinetic mechanism studies further disclose that the cooperative catalytic function of two components, in particular the exclusive capability of PrPO4 to activate hydrogen, is responsible for the promoted hydrogenation transformation of biomass derivatives via a quick Langmuir–Hinshelwood process over (PrPO4)m/Ni2P. These findings imply that an easily obtainable, cost-affordable and robust rare earth phosphate like present PrPO4 could be a potential replacement catalytic component for the traditional metal catalyst in the hydrogenation transformation reactions of biomass derivatives, which was also worth noting as a new kind of basic material for other green mass-transformation techniques involving hydrogen activation processes such as corresponding optical and electrical transformations.