The output of bio-based polyvinyl alcohol (PVA) has been growing rapidly with a substantial increase of developments both in academic and industrial research areas in the past decade, which is due to its water solubility, plasticity, and degradability. However, PVA is highly flammable with a limiting oxygen index of only 19% owning to its inherent macromolecular structure composed of carbon, hydrogen, and oxygen atoms. The demand for flame retardancy of PVA has been increased rapidly and is generally satisfied by introducing flame retardants via chemical grafting, physical blending, and coating. This review summarizes the flame retardants applied in PVA and their influence on the flammability and mechanical properties of PVA materials. The type of flame retardant additives and their application technologies for various PVA products are presented in terms of various PVA products, such as films, aerogel, fibers, foams, and bulk composites. The films dominate the whole research of flame retardant PVA materials owing to their widespread application. The fire performance and flame retardant mechanism are compared and discussed. Additionally, PVA acted as an assistant agent in some polymeric flame-retardant formulations is also discussed and reviewed.