Al–air batteries can serve as a bridge for high-quality cyclic utilization of aluminum resources. However, limited insights into the spent electrolyte are challenging to accurately adjust the recovery process to obtain premium Al-containing products. Herein, the properties and composition of the spent electrolyte were explored through experiments and theoretical calculations. The results demonstrate that the viscosity of the spent electrolyte increased with the rise in discharge current density, time and temperature under highly alkaline conditions, while the ionic conductivity and causticity obviously decreased. Al(OH)₄⁻ was the prime and balanced aluminate species when the battery was discharged at 25 °C and coexisted with a bit of [Al₂O(OH)₆]²⁻, [Al₂O₂(OH)₆]⁴⁻ and Al(OH)₆³⁻ ions. Especially, the characteristics of the spent electrolyte were mainly dominated by the discharge time and temperature when the current density was continuously increased. There was only Al(OH)₄⁻ in the electrolyte at a higher discharge temperature. The DFT results also reveal that the polynuclear aluminate ions were produced by the interaction between the mononuclear aluminate ion Al(OH)₄⁻ and OH⁻. This work manifests a profound insight into the spent electrolyte from Al–air batteries for the efficient recycling of aluminum resources.