The rational design of high-efficiency catalysts is hindered by the knowledge of active sites, which always experience dynamic transformations within different time scales. In this regard, tracking these time-dependent processes is essential to building the correlation between the active site and catalytic performance. Achieving this goal requires powerful characterization techniques to overcome the obstacle induced by the time mismatch. By virtue of the local structure sensitivity, synchrotron X-ray absorption spectroscopy (XAS) comprising step-scanning XAS, quick-scanning XAS, and energy-dispersive XAS has been widely applied to record structural evolution events. In this Perspective, we highlight the substantial accomplishments achieved by these time-resolved XAS techniques. Their principles, advantages, and limitations involved in monitoring energy-involving electrocatalysis were also introduced. Meanwhile, the key challenges that we are encountering and the further directions of time-resolved XAS are also provided. We sincerely hope that these insights could offer a reliable guideline for other researchers to design more efficient in situ experiments.