Oxidized cellulose nanofibers (CNF), embedded in an electrospun polyacrylonitrile (PAN) nanofibrous scaffold, were grafted with cysteine to increase the adsorption capability for chromium (VI) and lead (II). Thiol-modified cellulose nanofibers (m-CNF) were characterized by titration, FT-IR, energy dispersive spectroscopy (EDS) and SEM techniques. Static and dynamic Cr(VI) and Pb(II) adsorption studies of m-CNF nanofibrous composite membranes were carried out as a function of pH and of contact time. The results indicated these membranes exhibited high adsorption capacities for both Cr(VI) (87.5 mg/g) and Pb(II) (137.7 mg/g) due to the large surface area and high concentration of thiol groups (0.9 mmol of –SH/gram m-CNF). The morphology and property of m-CNF nanofibrous composite membranes was found to be stable, and they could be used and regenerated multiple times with high recovery efficiency.