Crystal structure determines electrochemical energy storage characteristics; this is the underlying logic of material design. To date, hundreds of electrode materials have been developed to pursue superior performance. However, it remains a great challenge to understand the fundamental structure–performance relationship and achieve quantitative crystal structure design for efficient energy storage. In this review, we introduce the concept of crystal packing factor (PF), which can quantify crystal packing density. We then present and classify the typical crystal structures of attractive cathode/anode materials. Comparative PF analyses of different materials, including polymorphs, isomorphs, and others, are performed to clarify the influence of crystal packing density on energy storage performance through electronic and ionic conductivities. Notably, the practical electronic/ionic conductivities of energy storage materials are based on their intrinsic characteristics related to the PF yet are also affected by extrinsic factors. The PF provides a novel avenue for understanding the electrochemical performance of pristine materials and may offer guidance on designing better materials. Additional approaches involve size regulation, doping, carbon additives, and other methods. We also propose extended PF concepts to understand charge storage and transport behavior at different scales. Finally, we provide our insights on the major challenges and prospective solutions in this highly exciting field.