As a fully degradable polymer, polyvinyl alcohol (PVA) is widely used in the preparation of natural polymer composite biodegradable materials with good chemical stability, filming properties and biocompatibility. The research progresses of starch/PVA materials, cellulose/PVA materials, chitosan/PVA materials, lignin/PVA materials and protein/PVA materials are reviewed, and the prospect of biodegradable composites substituting for some traditional plastics is proposed as well.