By connecting a column electrolysis method with a stopped-flow technique, a pulse-electrolysis stopped-flow method has been developed. This method has many advantages that it can be applied to the detection and characterization of unstable intermediates as well as the analysis of the reaction kinetics of heterogeneous electrode reactions as homogeneous reactions. In addition, this method can be utilized combined with various spectroscopic methods including UV-visible, resonance Raman (RR) and electrogenerated chemiluminescence (ECL) measurements. In this review, the advantages of this method are demonstrated with many successful results in the analyses of the reaction kinetics and mechanisms involving electrogenerated species obtained by using the pulse-electrolysis stopped-flow method.