The heterogeneous catalytic reduction of Cr(VI) to Cr(III) is an effective strategy for aqueous Cr(VI) contamination abatement, which requires the development of highly efficient, low-cost, and recyclable catalysts. Herein, Ni2P/N-doped biocarbon composites (Ni2P/N-BC) were fabricated through an anoxic pyrolysis process using NaCl and KCl as activators. A precursor of yeast biomass provided the essential C, N, and P elements for Ni2P/N-BC formation. When adopted for Cr(VI) reduction in the presence of oxalic acid as a reductant, the fabricated Ni2P/N-BC performed superior catalytic activity with a 100% Cr(VI) reduction efficiency within 10 min (Ni2P/N-BC-5 = 0.2 g L-1, oxalic acid = 0.4 g L-1, Cr(VI) = 20 mg L-1). Typical affecting parameters, e.g., catalyst dosage, oxalic acid loading, reaction temperature, initial solution pH, and water matrix, were investigated. Ni2P/N-BC exhibited good applicability in a broad pH range from 3.0 to 9.0 and in actual aquatic systems. Cr(VI) reduction efficiency remained 92.7% after five recycle runs. Such promising catalytic activity may originate from the well-crystallized Ni2P, N-doped biocarbon framework and high specific surface area of the materials. Preliminary reaction mechanism analysis indicated that the favorable charge state of Ni2P, fast hydrogen transfer, affinity of oxalic acid to Cr(VI), and inherent electron transfer in the biocarbon matrix contributed to effective Cr(VI) reduction. This work not only provides a facile and low-cost strategy to construct Ni2P/N-doped biocarbon nanosheet composite using environmentally benign biomass but also brings new insights for the remediation of Cr(VI) contamination.