An ethanol-responsive poly(vinylidene difluoride) (PVDF) membrane with poly(N-isopropylacrylamide) (PNIPAM) nanogels as functional gates is prepared via vapor-induced phase separation (VIPS). The introduction of PNIPAM nanogels leads to generation of cellular-like membrane pores from a bicontinuous structure. The water permeability and mechanical strength of blank PVDF membranes are higher than those formulated by the liquid-induced phase separation process. The blended membranes exhibit satisfactory ethanol-responsive and thermo-responsive characteristics. The operation temperature and the content of PNIPAM nanogels in the blended membranes significantly influence the ethanol-responsive characteristics.