Biological H2 production offers distinctive advantages for environmental protection over existing physico-chemical methods. This study focuses specifically on hydrogenases, a class of enzymes that serves to effectively catalyze H2 formation from protons or oxidation to protons. It reviews the classification schemes (i.e., [NiFe]-, [FeFe]-, and [Fe]-hydrogenases) and properties of these enzymes, which are essential to understand the mechanisms for H2 production, the control of cell metabolism, and subsequent increases in H2 production. There are five kinds of biological hydrogen production methods, categorized based upon the light energy requirement, and feedstock sources. The genetic engineering work on hydrogenase to enhance H2 production is reviewed here. Further discussions in this study include nitrogenase, an enzyme that normally catalyzes the reduction of N2 to ammonia but is also able to produce H2 under photo-heterotrophic conditions, as well as other applicable fields of hydrogenase other than H2 production.