The pulse radiolysis technique is based on a perturbation of a system by a short pulse (<1μsec) of high energy radiation. This technique has been employed for the study of the mechanism of action of the oxidation-reduction proteins with high time resolution. This review deals with studies of pulse radiolisis in biological systems: (1) principles, (2) experimental methods, (3) examples, and (4) the mechanism of reduction of electron transfer proteins by hydrated electron (eaq-). The eaq- reacts with the redox site of electron transfer protein good yield, compared with other proteins. This reduction is assigned mainly to a direct reaction proceeding via the exposed edge of the redox site. In other cases, eaq- does not reduce the redox site in the protein and reacted with the amino acid residues. These results suggests that electron captured by the protein does not necessarily migrate the redox site in the protein.