a b s t r a c tToday, the reduction of nitro aromatics stands a major challenge because of the pollutant and detrimental nature of these compounds. In the present study, we show that nickel(0) nanoparticles (Ni-NP) decorated on electrospun polymeric (polycaprolactone(PCL)/chitosan) nanofibers (Ni-NP/ENF) effectively catalyze the reduction of various nitrophenols (2-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) under mild conditions. Ni-NP/ENF nanocatalyst was reproducibly prepared by deposition-reduction technique. The detailed characterization of these Ni-NP/ENF based nanocatalyst have been performed by using various spectroscopic tools including ICP-OES, P-XRD, XPS, SEM, BFTEM, HRTEM and BFTEM-EDX techniques. The results revealed the formation of well-dispersed nickel(0) NP (d mean = 2.71-2.93 nm) on the surface of electrospun polymeric nanofibers. The catalytic activity of the resulting Ni-NP/ENF was evaluated in the catalytic reduction of nitrophenols in aqueous solution in the presence of sodium borohydride (NaBH 4 ) as reducing agent, in which Ni-NP/ENF nanocatalyst has shown high activity (TOF = 46.2 mol 2-nitrophenol/mol Ni min; 48.2 mol 2,4-dinitrophenol/mol Ni min; 65.6 mol 2,4,6-trinitrophenol/mol Ni min). More importantly, due to the nanofibrous polymeric support, Ni-NP/ENF has shown a flexible characteristics along with reusability property. Testing the catalytic stability of Ni-NP/ENF revealed that this new catalytic material provides high reusability performance (at 3rd reuse 86% for 2-nitrophenol, 83% 2,4-dinitrophenol and 82% 2,4,6-trinitrophenol) for the reduction of nitrophenols even at room temperature and under air. The present study reported here also includes the compilation of wealthy kinetic data for Ni-NP/ENF catalyzed the reduction of nitrophenols in aqueous sodium borohydride solution depending on temperature and type of support material (Al 2 O 3 , C, SiO 2 ) to understand the effect of the support material and determine the activation parameters.