Abstract Carbon‐free dual‐atom catalysts (CFDACs) are beginning to make their presence in the field of electrocatalysis due to their unique properties and structures that are different from those of carbon‐based DACs, which are endowed with different activity, selectivity, and stability. Currently, some advances are made in the study of CFDACs, including structure‐performance relationships of metal‐support interaction, theoretical study combined with experiments, electrocatalytic applications with potential catalytic mechanisms, and design strategies to achieve highly active electrocatalytic performance. Herein, the perception of the structure‐performance relationships of CFDACs is first elaborated in terms of carbon‐free substrates and dual‐atom sites, then briefly summarizes advanced characterization techniques, theoretical study, and energy storage and conversion applications, and highlights the strategies to realize the design of high‐performance CFDACs in terms of vacancy anchoring, strain regulation, and alloying, and finally put forward the personal viewpoints on the current challenges and future development of CFDACs.