Organosilicon compounds play important roles in organic chemistry and pharmaceutical applications. Therefore, increasing attention has been focused on the preparation of organosilicon compounds with desired chemical and physical properties by the effective biocatalysts. This article outlines the bioconversion of organosilicon compounds by the use of biocatalysts such as microorganisms, alcohol dehydrogenases, hydrolases, and hydroxynitrile lyases. The preparation of silicon‐containing amino acids and cyanohydrins by the bioconversion is also described. Furthermore, the effects of silicon atom on the enzymatic reaction are discussed with comparative studies by using organosilicon compounds and corresponding carbon compounds as substrates of enzymes.