Polyvinyl alcohol (PVA) is widely used in home textiles, coatings, industrial materials and other fields. Unfortunately, its flammability limits its application, so research into enhancing its flame-retardant properties has attracted widespread attention in recent years. In this work, a α-zirconium phosphate (α-ZrP)/cerium phosphate (CPO)/graphene oxide (GO) nanocomposite (ZCG) flame-retardant material was prepared using a hydrothermal method. The microstructure and composition of the composite were analyzed in detail, showing that hexagonal flakes of α-ZrP were attached on the surface of CPO rods. An intumescent, flame-retardant system consisting of ammonium polyphosphate (APP) with ZCG was fabricated to produce flame-retardant polyvinyl alcohol. The effects of the intumescent flame-retardant-based ZCG composite on the flame-retardant properties and thermal stability of PVA were investigated. The results revealed that the PVA/APP/ZCG composites have better flame retardancy, and that PVA and ZCG synergistically enhance the flame retardancy of the composite material.