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The demand for electrical energy storage (EES) is ever increasing, which calls for better batteries. NASICON‐structured materials represent a family of important electrodes due to its superior ionic conductivity and stable structures. A wide range of materials have been considered, where both vanadium‐based and titanium‐based materials are recommended as being of great interest. NASICON‐structured materials are suitable for both the cathode and the anode, where the operation potential can be easily tuned by the choice of transition metal and/or polyanion group in the structure. NASICON‐structured materials also represent a class of solid electrolytes, which are widely employed in all‐solid‐state ion batteries, all‐solid‐state air batteries, and hybrid batteries. NASICON‐structured materials are reviewed with a focus on both electrode materials and solid‐state electrolytes.