Dual-layered composite nanofibrous membrane equipped with electrical conduction, magnetism and photoluminescence trifunctionality is constructed via electrospinning. The composite membrane consists of a polyaniline (PANI)/Fe3O4 nanoparticles (NPs)/polyacrylonitrile (PAN) tuned electrical magnetic bifunctional nanofibrous layer at one side and a Eu(TTA)(3)(TPPO)(2)/polyvinylpyrrolidone (PVP) photoluminescent nanofibrous layer at the other side, and the two layers are tightly combined face-to-face together into the novel dual-layered composite membrane with trifunctionality. The electric conductivity and magnetism of electrical magnetic bifunctionality can be respectively tunable via modulating the respective PANI and Fe3O4 NPs contents, and the highest electric conductivity approaches the order of 1 x 10(-2) S cm(-1). Predominant red emission at 615 nm can be obviously observed in the photoluminescent layer under 366 nm excitation. Moreover, the luminescent intensity of photoluminescent layer is almost unaffected by the electrical magnetic bifunctional layer because of the fact that the photoluminescent materials have been successfully isolated from dark-colored PANI and Fe3O4 NPs. The novel dual-layered composite nanofibrous membrane with trifunctionality has potentials in many fields. Furthermore, the design philosophy and fabrication method for the dual-layered multifunctional membrane provide a new and facile strategy toward other membranes with multifunctionality.