The significant volume of existing buildings and ongoing annual construction of infrastructure underscore the vast potential for integrating large-scale energy storage solutions into these structures. Herein, we propose an innovative approach for developing structural and scalable energy storage systems by integrating safe and cost-effective zinc-ion hybrid supercapacitors into cement mortar, which is the predominant material used for structural purposes. By performing air entrainment and leveraging the adverse reaction of the ZnSO₄ electrolyte, we can engineer an aerated cement mortar with a multiscale pore structure that exhibits dual functionality: effective ion conductivity in the form of a cell separator and a robust load-bearing capacity that contributes to structural integrity. Consequently, a hybrid supercapacitor building block consisting of a tailored cement mortar, zinc metal anode, and active carbon cathode demonstrates exceptional specific energy density (71.4 Wh kg⁻¹ at 68.7 W kg⁻¹), high areal energy density (2.0 Wh m⁻² at 1.9 W m⁻²), favorable cycling stability (∼92% capacity retention after 1000 cycles), and exceptional safety (endurance in a 1-hour combustion test). By demonstrating the scalability of the structural energy storage system coupled with solar energy generation, this new device exhibits great potential to revolutionize energy storage systems.