In this work, a novel electrospun chitosan (CS)/polyvinylpyrrolidone (PVP)/polyvinyl alcohol (PVA) nanofibrous membrane was prepared to remove heavy metal ions and organic pollutants from water. The nanofiber morphologies were adjusted through the optimal electrospinning process parameters. Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterizations indicated that a well-crosslinked CS/PVP/PVA nanofiber film was formed. Under the optimize conditions, the obtained CS/PVP/PVA nanofiber membranes exhibited porous and uniform nanofibrous structures with an average diameter of 160 nm and a pure water permeability of 4518.91 L·m·h·bar. In addition, the adsorption and separation performance of CS/PVP/PVA nanofiber membranes were evaluated with Cu(II), Ni(II), Cd(II), Pb(II) and Methylene Blue (MB), Malachite Green (MG) as target ions and dyes. The results showed that the retention rate of CS/PVP/PVA nanofiber membranes for Cu(II), Ni(II), Cd(II), Pb(II), MG and MB can reach 94.20%, 90.35%, 83.33%, 80.12%, 84.01% and 69.91%, respectively. The adsorption capacities of Cu(II), Ni(II), Cd(II), Pb(II), MG and MB were 34.79, 25.24, 18.07, 16.05, 17.86 and 13.27 mg g. The adsorption kinetics of heavy metal ions and dyes by the nanofiber membranes can be explained by the Langmuir isotherm model and represented by the pseudo-second-order kinetic mechanism that determined the spontaneous chemisorption process. This study provides a synthetic approach to membranes for the removal of organic and heavy metal micropollutants from water.