A novel beta-cyclodextrin/poly(vinyl alcohol) nanofibrous membrane (beta-CD/PVA(nfm)) with the function of molecular capture was successfully prepared by electrospinning homogeneous aqueous solutions of beta-CD and PVA. beta-CD/PVA(nfm) was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. The viscosity of beta-CD/PVA solution was increased with the concentration of beta-CD and high viscosity of beta-CD/PVA solution was beneficial to form more uniform nanofibers. The interaction between beta-CD and PVA in the solution was studied by rheological measure and (1)H NMR spectra. The rheological change of electrospinning solutions was attributed to the intermolecular hydrogen bonding between beta-CD and PVA in the solution, which was confirmed by (1)H NMR spectra. The electrochemical measurement showed that beta-CD/PVA(nfm) could recognize small hydrophobic molecules such as ferrocene (Fc) by forming inclusion complexes. The molecular capturing ability of beta-CD/PVA(nfm) was increased with the amount of beta-CD in composite nanofibrous membrane. The results suggested that the composite nanofibrous membrane was potentially applied to purification/separation processes, electrochemical sensor, drug delivery, and so on. (C) 2011 Elsevier Ltd. All rights reserved.