Gold nanoparticles (AuNPs) have attracted widespread attention for their excellent catalytic activity, as well as their unusual physical and chemical properties. The main challenges come from the agglomeration and time-consuming separation of gold nanoparticles, which have greatly baffled the development and application in liquid phase selective reduction. To solve these problems, we propose the preparation of polyvinyl alcohol(PVA)/poly(acrylic acid)(PAA)/Fe3O4 nanocomposites with loaded AuNPs. The obtained PVA/PAA/Fe3O4 composite membrane by electrospinning demonstrated high structural stability, a large specific surface area, and more active sites, which is conducive to promoting good dispersion of AuNPs on membrane surfaces. The subsequently prepared PVA/PAA/Fe3O4@AuNPs nanocomposites exhibited satisfactory nanostructures, robust thermal stability, and a favorable magnetic response for recycling. In addition, the PVA/PAA/Fe3O4@AuNPs nanocomposites showed a remarkable catalytic capacity in the catalytic reduction of p-nitrophenol and 2-nitroaniline solutions. In addition, the regeneration studies toward p-nitrophenol for different consecutive cycles demonstrate that the as-prepared PVA/PAA/Fe3O4@AuNPs nanocomposites have outstanding stability and recycling in catalytic reduction.