In this work, we prepare a poly(vinyl alcohol-co-ethylene) (PVA-co-PE) nanofibrous membrane supported Ni-P nanocatalyst via a melt-phase-separated nanofiber-suspension coating followed by nickel electroless deposition with sodium hypophosphite as the reducing agent. The morphology and structure analysis show that the PVA-co-PE nanofibrous membranes (NFM) are decorated by the coating of nickel based nanoparticles on the surface of nanofibers, which is a mixture of Ni and Ni3P with about 30 nm average nanoparticle size. The 3D nanofibers' scaffold with 4.55 g/m(2) nanofiber coverage density (pore size: 180 nm) affords a best deposited substrate for Ni-P nanoparticles to hydrogenate p-nitrophenols (PNP). The supported catalysts exhibit high catalytic rate constant 18.04 x 10(-3) s(-1), 26.84 x 10(-3) s(-1) and 19.40 x 10(-3) s(-1) at 20 degrees C when Ni-P loading content is 50 wt.%, 25 wt.% and 14 wt.%, respectively. Furthermore, the catalytic materials present an excellent recoverable and cyclic feature that still over 98% conversion of PNP after 6 times. The outstanding performance obtained here can be attributed to phosphorous doped nanostructure of nickel catalyst, 3D microstructure of nanofibrous membrane and the synergistic effect of nano Ni-P and membrane, including high specific area for holding Ni-P atoms, plenty of electron holes for adsorbing organic molecules, and good conductivity for electron transfer between each decorated nanofibers. Moreover, present Ni-P-based catalyst is relatively cheap, stable and direct separable, implying its superiority in hydrogenation of nitrophenols to aminophenols. (C) 2016 Elsevier B.V. All rights reserved.