Ice‐templating, a versatile manufacturing process, is widely utilized to create porous materials by freezing aqueous solutions. Notably, this technique is material independent, allowing for the fabrication of microstructured bulk or sheet materials of ceramic, glass, metal, polymer, and composite materials. Herein, the influence of freeze‐cast zinc electrodes on zinc–air batteries is investigated. The analysis includes the charge and discharge cycling behavior of pure powder, gel matrix, and sintered freeze‐cast zinc electrodes, complemented by the study of the distribution of relaxation times. Remarkably, the best cycling performance is achieved with the combination of a gel electrolyte and a freeze‐cast zinc electrode, highlighting the potential significance of this microstructure–electrolyte pairing for enhancing the performance of zinc–air batteries.