The design and self-assembly of graphene oxide (GO)-based composite membranes have attracted enormous attention due to their wide application in nanomaterial and environmental fields. In this work, we have successfully developed a strategy to fabricate new composite membranes based on poly(vinyl alcohol)/poly(acrylic acid)/carboxyl-functionalized graphene oxide modified with silver nanoparticles (PVA/PAA/GO-COOH@AgNPs), which were prepared via thermal treatment and the electrospinning technique. Due to the strong pi-pi forces and strong electrostatic interactions of GO-COOH sheets, the prepared composite membranes and their lager surface areas were modified by scores of AgNPs, which demonstrated that a high-efficiency photocatalyst removed the organic dyes from the aqueous solutions. The prepared PVA/PAA/GO-COOH@AgNPs nanocomposite membranes showed a remarkable photocatalytic capacity in the catalytic degradation of the methylene blue dye solutions. Most importantly, the whole process was easy, mild, and eco-friendly. Additionally, the as-prepared membranes could be repeatedly used after the catalytic reaction.