As the global energy structure evolves and clean energy technologies advance, electrocatalysis has become a focal point as a critical conversion pathway in the new energy sector. Transitional metal electrocatalysts (TMEs) with their distinctive electronic structures and redox properties show great potential in electrocatalytic reactions. However, complex reaction mechanisms and kinetic limitations hinder the improvement of energy conversion efficiency, highlighting the necessity for comprehensive studies on structure and performance of electrocatalysts. X-ray Absorption Fine Structure (XAFS) spectra stand out as a robust tool for examining the electrocatalyst's structures and performance due to its atomic selectivity and sensitivity to local environments. This review delves into the application of XAFS technology in characterizing TMEs, providing in-depth analyses of X-ray Absorption Near-Edge Structure (XANES) spectra, and Extended XAFS (EXAFS) spectra in both R-space and k-space. These analyses reveal intrinsic structural information, electronic interactions, catalyst stability, and aggregation morphology. Furthermore, the paper examines advancements in in-situ XAFS techniques for real-time monitoring of active site changes, capturing critical intermediate and transitional states, and elucidating the evolution of active species during electrocatalytic reactions. These insights deepen our understanding on structure-activity relationship of electrocatalysts and offer valuable guidance for designing and developing highly active and stable electrocatalysts.