Abstract: The composition, structure and accumulation of rice starch are key factors affecting grain quality and yield. Therefore, the key enzymes involved in the formation of rice starch need to be studied. With the development of molecular biology techniques, research into rice starch quality has made extensive progress. This review summarizes the progress of these key enzymes, including ADP-glucose pyrophosphorylase, starch synthase, starch branching enzyme and de-branching enzyme, and their roles involved in rice starch biosynthesis. Prospects for future research are also discussed.