Electrocatalysis plays a crucial role in energy conversion and storage, providing an effective way to achieve the goals of carbon neutrality. The combination of electrochemical methods with advanced spectroscopy techniques gives an insightful and in-depth understanding of electrocatalysis and the structure–performance relationship of catalysts. In this review, the recent advances of spectroscopy techniques are summarized with a focus on the electronic structure of electrocatalysts and the relevant dynamical reaction processes, and further research challenges and developments are outlined for spectroscopy techniques in the field of energy electrocatalysis.