A new thin film nanofibrous composite (TFNC) membrane for Cr (VI) removal was prepared by layer-by-layer assembly of chitosan/alginate on the surface of the electrospinning nanofibrous substrates. Scanning electron microscopy and static contact angle measurement were applied to characterize surface morphology and hydrophilicity, respectively. The mechanism of Cr (VI) removal and some factors, including positive/negative charge of terminating layer, bilayers, and Cr (VI) concentration, were investigated by a dead-end filter. These TFNC membranes exhibited a high Cr (VI) removal efficiency and an advantage of saving energy (the operating pressure was only 0.7 bar). The high efficiency was supposed to be the adsorption and Donnan effect which acted simultaneously for Cr (VI) removal. Besides, the research of recyclable property indicated that these TFNC membranes were easily regenerated and had a stable recycle property. Additionally, simple fabrication, low cost, and abundant species of polyelectrolytes showed these membranes had a good potential in heavy metal removal. POLYM. ENG. SCI., 2014. © 2014 Society of Plastics Engineers