Enzymatic redox reactions for the oxidation (or reduction) of the substrates use organic dyes or metal complexes as electron acceptors (or donors), which can be regenerated by electrochemical reactions of the compounds at an electrode surface. This type of coupling of the enzymatic reactions with the electrochemical reactions is called bioelectrocatalysis and allows us to measure the enzymatic reactions by an electrochemical method. The enzyme-electrochemical method provides a new technique for investigating a variety of biological redox reactions and for applying the reactions to biosensors, bioreactors, and biofuel cells. The bioelectrocatalysis-based research works are described here. First, a new method of protein redox potential measurements and a novel electrochemical kinetic analysis of oxidoreductase reactions are described. Second, a new methodology of characterizing microbial catalytic activities is presented. In the last, applications to the constructions of biosensors, bioreactors, and biofuel cells are mentioned.