Industrial waste can be reduced by microorganisms to produce hydrogen,its mechanism can be divided into two parts:biophotolysis and fermentation.Light is utilized by the former,while the organic compound and the electron produced in the metabolism are utilized by the latter.Hydrogenases are the key enzymes in the process of biohydrogen production,and catalyze the oxidation of hydrogen and the reduction of protons.[NiFe] hydrogenase and [Fe] hydrogenase are the main types of hydrogenases and have different structures but similar catalytic mechanism.This paper summarizes the types of hydrogen-producing microbes,the research on biohydrogen metabolism and the catalytic mechanism of hydrogenase,and brings forward the prospect.