The problem of water pollution has become increasingly serious, and it has already threatened the survival of mankind and has become an obstacle to the healthy development of human health. Here, we prepared a novel polyvinyl alcohol (PVA)/polyacrylic acid (PAA)/MXene fiber membrane by electro-spinning. After heat treatment of film and subsequent modification with Pd nanoparticles, PVA/PAA/MXene@PdNPs composite nanofiber membrane with high specific surface area and excellent catalytic performance was finally prepared. The uniform distribution of MXene sheets in the composite fiber membrane not only solves the problem that the MXene sheet is not easy to be monolayerized, but also can grow the self-reduced Pd nanoparticles on the MXene sheets. In addition, the composite nanofiber membrane exhibits excellent catalytic ability and cycle stability for 4-nitrophenol (4-NP) and 2-nitrophenol (2-NA), providing new strategy for the study of catalytic composite materials related to degradation of wastewater.