Compared with traditional chemical catalysis or enzymatic synthesis, chemoenzymatic relay reaction is a simpler, more efficient and economical method. It not only has the advantages of high efficiency and selectivity of enzyme catalysis, but also has the advantages of low price of synthetic raw materials, simple and high efficiency of synthetic process, green and friendly production environment, and excellent optical purity of the obtained product. Thus, chemoenzymatic relay synthesis methods have been widely used in the synthesis of high-value chiral compounds. In recent years, chemists have been committed to making chemoenzymatic catalytic conditions easier by changing catalysts and designing more reasonable ways, which could be used in more fields. In this review, the recent progress in the synthesis of chiral alcohols, epoxides, heterocyclics and other chiral compounds by using chemoenzymatic relay synthesis, such as enzyme and metal catalysis, enzyme and organic catalysis, enzyme and new reaction techniques, is reviewed, and the development trends of this field are also prospected. Keywords chemoenzymatic; relay reaction; high-value chiral compound; enzyme-metal catalysis; enzyme-organic catalysis