The need for pollution control and the depletion of non-renewable energy sources have made the development of clean energy an urgent need for society. Electrochemical energy technology can efficiently convert chemical energy into electric energy without producing pollutants, which arouses researchers’ interest in recent days. The development of this technology relies heavily on the development of suitable catalysts. However, the study of the reaction mechanism at the solid-liquid interface is difficult due to the complexity of the reactions, the variety of intermediates, their low content and the short duration of their existence, which further limits the development of catalysts. Surface-enhanced Raman spectroscopy, as a molecular fingerprint spectrum, is able to obtain strong and sensitive Raman scattering signals and thus provide good structural information on molecules at the electrode surface interface. This paper focuses on the application of surface-enhanced Raman spectroscopy to the study of the reaction mechanism of fuel cells and lithium batteries. Firstly, this article will introduce the research on the mechanism of enhancing the reaction of intermediate species in fuel cell energy reactions ORR and HOR by surface-enhanced Raman spectroscopy. Secondly, it will introduce the mechanism of electrode reactions and dynamic processes at the solid-liquid interface of lithium batteries through similar strategies using surface-enhanced Raman spectroscopy. Finally, it will summarize the shortcomings of surface-enhanced Raman spectroscopy in the application of electrocatalytic reactions and make future prospects.