The incorporation of atomic scale defects, such as cation vacancies, in electrode materials is considered an effective strategy to improve their electrochemical energy storage performance. In fact, cation vacancies can effectively modulate the electronic properties of host materials, thus promoting charge transfer and redox reaction kinetics. Such defects can also serve as extra host sites for inserted proton or alkali cations, facilitating the ion diffusion upon electrochemical cycling. Altogether, these features may contribute to improved electrochemical performance. In this review, the latest progress in cation vacancies‐based electrochemical energy storage materials, covering the synthetic approaches to incorporate cation vacancies and the advanced techniques to characterize such vacancies and identify their fundamental role, are provided from the chemical and materials point of view. The key challenges and future opportunities for cation vacancies‐based electrochemical energy storage materials are also discussed, particularly focusing on cation‐deficient transition metal oxides (TMOs), but also including newly emerging materials such as transition metal carbides (MXenes). This review summarizes the synthetic approaches to incorporate cation vacancies for metal oxides/carbides, the advanced techniques to characterize such vacancies, and the investigations of their fundamental roles in enhancing electrochemical performance. Discussions of the remaining key challenges for the design of high‐performance cationdeficient metal oxides/carbides alongside an analysis of future opportunities.