The preparation and oxygen sensing properties of luminescence quenching oxygen sensing materials based on an electrospum composite nanofibers with [Cu(POP)DPPZ]BF4(POP = bis[2-(diphenylphosphino)phenyl]ether; DPPZ = dipyrido[2,3-a:3',2'-c]phenazine) complex embedded within polystyrene (PS) matrix are described in this article. The luminescence of [Cu(POP)DPPZ]BF4 complex within the electrospum nanofibers can be efficiently quenched by oxygen with good sensitivity (I0/I100 = 5.54) and rapid response (3 s), which suggests that the Cu(I) complex/polystyrene composite nanofibers presented in this article can be used for developing oxygen sensors. The downward oxygen sensing Stern-Volmer plots can be attributed to the heterogeneous environment of the Cu(I) luminophore within the nanofibers. The high sensitivity is attributed to the low-dimensional structure of the nanofiber and its large surface area-to-volume ratio, which facilitates oxygen entry and diffusion.