Polyoxometalates (POMs) had a diverse structure and composition and unique performance characteristics. It was considered as a promising class of anionic materials in electrochemical biosensors and many other fields. POMs had defects such as poor electrical conductivity and low specific surface area. The preparation of POMs into polyoxometalate-based complexes with nanomaterials such as carbon-based materials, noble metals and metal organic frameworks could improve the defects of POMs and and enhance its electrocatalytic properties. Polyoxometalate-based complexes will also expand the range of applications in the field of electrochemical biosensors. This article reviewed the types and preparation methods of electrochemical biosensors with polyoxometalate-based complexes. As well as its research progress in the field of food analysis, and the future challenges and application prospects of this complexes were discussed.