The temperature-responsive tri-copolymer (PNNS) i.e. poly(N-isopropylacrylamide-co-N-hydroxymethylacrylamide-co-octadecyl acrylate) with number-average molecular weight of 2.24×10⁴ g/mol and lower critical solution temperature of 35.8℃ was firstly synthesized via solution free radical polymerization, and then the chemical structure of which was confirmed by nuclear magnetic resonance spectrometer, and thereby the measured molar ratio of its three substances is 100∶27∶5. The hollow nanofibrous membrane with high stability in aqueous medium were prepared by coaxial electrospinning technique using the ethanol and water solution of PNNS as shell spinning solution and mineral oil as core spinning solution, followed by the processes of heat treatment and extracting the oil by toluene. Results show the membrane component of nanofibers presents hollow structure, of which the shell thickness gradually decreases with the increase of the flow rate of the core spinning fluid; The membrane in aqueous medium shows remarkable temperature-responsiveness; When the aqueous medium temperature is raised from 25℃ to 50℃, the percentage of area shrinkage of the membrane reaches above 50%; When the aqueous medium temperature changes alternately between 25℃ and 50℃, the hollow nanofibrous membrane may experience swelling and deswelling alternatively, but it could reach an equilibrium within 10s for the two cases.