The urgent demand for cost‐effective energy storage devices for large‐scale applications has led to the development of several beyond‐lithium energy storage systems (EESs). Among them, calcium‐ion batteries (CIBs) are attractive due to abundant calcium resources, excellent volumetric and gravimetric capacities of Ca metal anode, and potential high energy density coming from the multivalent feature of Ca‐ion. Therefore, the exploration of CIBs electrode materials and the construction of CIBs devices are gaining increasing research interest. Relevant publications cover a wide range of materials by both theoretical and experimental investigations, whereas the performances of rocking‐chair CIBs have been unsatisfactory. Meanwhile, multi‐ion strategies using more than one ion as the charge carrier have been demonstrated to be feasible and promising options in realizing room temperature CIBs. The summary and reflection of previous studies would provide useful information for future exploration and optimization. In this circumstance, this paper overviews the reported CIBs electrode materials, including both anode and cathode, and presents the latest progress of multi‐ion strategies in CIBs. Fundamental challenges, potential solutions, and opportunities are accordingly proposed, mimicking other more mature EESs. This review may promote the development of electrode materials and accelerate the construction of low‐cost and high‐performance CIBs. Ca‐ion based technologies are attractive for low‐cost, high‐performance energy storage, while their development is currently far from practical applications. An overview of the key electrode materials for Ca2+ storage and a comprehensive insight of promising optimization strategies such as the multi‐ion strategy are critical to promote further development of Ca2+ technologies.