With aim of constructing a class of functional environmentally friendly materials, we electrospun chitosan (CS) blends with various contents of poly(ethylene oxide) (PEO) into a series of composite nanofibrous membranes exhibiting shape-memory behaviors. In the present composite system, CS and PEO served as hard and soft domains, respectively. The CS, presenting no thermal transition, and the PEO, with apparent melting-crystallization, were demonstrated by differential scanning calorimetry testing. Characterizations also revealed that the morphologies of the CS/PEO membranes were controlled by the mass ratios of CS/PEO. The composite fibrous membranes showed great mechanical performances and thermal stabilities as well. Moreover, CS/PEO possessed excellent shape-memory behaviors. Such fibrous membranes could complete their shape-recovery processes within 20 s at the temperature of 20 degrees C above the melting transition temperature (T-m). Both the shape fixity and shape-recovery ratios were higher than 90%, even after five cycles. The CS/PEO fibrous membranes present significant potential applications in the field of biotechnology and tissue engineering, such as in scaffolds and smart tubes. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42532.