Lysozyme (LY) exfoliated rectorite (REC) based electrospun nanofibrous membranes with enhanced bacterial inhibition ability and thermostability were fabricated via electrospinning. All the obtained membranes exhibited better fiber shape and three-dimensional structure, which could be observed by scanning electron microscopy. Energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, and Fourier transform infrared (FTIR) spectrum denoted the existence of LY and REC in the composite membranes. Besides, the FTIR results suggested that there were interactions between REC and polyvinyl alcohol (PVA)/LY chains. Small angle X-ray diffraction indicated that REC was exfoliated by PVA and LY chains. In addition, the exfoliation of REC was directly confirmed by transmission electron microscopy. According to Brunauer-Emmett-Teller surface area test results, PVA/LY/REC membranes had higher surface area than that of PVA/LY membranes. The performance tests showed that both the thermal stability and antibacterial activity of the composite membranes were enhanced after adding REC. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41496.