Electrocatalysis has emerged as a pivotal field for sustainable energy and environmental solutions, fueling the development of diverse electrocatalysts over the past 2 decades. However, a comprehensive understanding of the intricate dynamical processes governing electrochemical reactions remains elusive and is hampering efficient catalyst design. Surfacesensitive techniques like in situ/operando Raman spectroscopy are indispensable for characterizing these dynamic processes and guiding the development of novel catalysts. This review systematically summarizes recent advances in employing in situ/operando Raman techniques, with a particular emphasis on surface-enhanced Raman spectroscopy (SERS), for probing various electrocatalytic systems. It discusses the development, advantages, and available configurations of these Raman techniques. Moreover, the review underscores the potential of in situ SERS in unraveling the intricate mechanisms of the oxygen evolution reaction (OER) through innovative strategies and methodological advancements. Notably, leveraging SERS for novel OER catalysts, such as single-atom catalysts, metal−organic frameworks, and electrolyte− electrode interfaces, can unveil unexplored reaction pathways, guiding the development of superior catalytic materials. Overcoming challenges and harnessing SERS' capabilities can deepen our mechanistic understanding of the OER, enabling the rational design of efficient and durable electrocatalysts crucial for renewable energy advancement.