Maize（Zea mays L.） starch biosynthesis is a highly complex process catalyzed by a series of enzymes.This article summarizes the existing literature on key enzymes in maize starch synthesis in recent years, systematically summarizes the roles of four key enzymes in starch synthesis, analyzes the regulatory factors of key enzymes in starch synthesis, and focuses on the characteristics and regulatory mechanisms of four key enzymes: ADP glucose pyrophosphorylase（AGPase）, starch synthase（SS）, starch branching enzyme（SBE）, and starch debranching enzyme（DBE）. Research indicates that multiple key enzymes cooperatively participate in maize starch synthesis, with their activities regulated by the expression of various genes. starch synthesis proceeds sequentially under the action of starch synthase, ADP-glucose pyrophosphorylase, starch branching enzyme, and starch debranching enzyme. Meanwhile, the functions of the four key enzymes are also regulated by the expression of various genes. By summarizing both domestic and international research on the key enzymes involved in maize starch synthesis, this review provides new insights and methodologies for improving starch synthesis and quality in maize.