Nanofibrous membranes of poly(D,L-lactic acid)/chitin blend were prepared by electro spinning for a barrier of guided tissue regeneration. A miscible solution was obtained by the blending chitin-salt complex into 1-methyl-2-pyrrolidone solution of poly(D,L-lactic acid). The properties of the blend were examined for nanofibrous fabrication. The viscosity of the blend solution was increased significantly due to chain entanglement despite the low ratio of chitin to poly(D,L-lactic acid). An interaction between two polymeric compositions was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction detected an appreciably ordered microstructure in the nanofiber of the blend. A membrane of thinner nanofibers was fabricated by electro spinning the chitin blend. The permeability of the membranes was examined using bioactive model compounds.