MXene as a kind of two-dimensional nanomaterial has aroused people's strong research interest because of its excellent properties. In the present study, we introduced a new poly(vinyl alcohol)/poly(acrylic acid)/FeO/MXene@Ag nanoparticle composite film fabricated by electrospinning and heat treatment as well as self-reduction reaction process. The obtained composite films showed high self-reduction ability because of the incorporation of MXene flakes. The intercalated MXene flakes in the composite nanofibers were evenly distributed, which not only solved the aggregation problem from MXene dispersion but also could self-reduce Ag nanoparticles in situ in composite materials. In addition, the composite nanofiber films exhibited good fiber structure, thermal stability, and magnetic properties. Moreover, the composite nanofiber films demonstrated excellent catalytic ability and cycle stability to 4-nitrophenol and 2-nitroaniline.