A rapid-charging aluminium-sulfur battery operating at 85°C with a quaternary molten salt electrolyte is reported. The electrolyte, a quaternary alkali chloroaluminate melt, facilitates fast Al³+ desolvation due to abundant high-order Al-Cl clusters and a low melting point. A nitrogen-functionalized porous carbon cathode mediates the sulfur reaction, enabling rapid-charging capability and excellent cycling stability with 85.4% capacity retention over 1400 cycles at 1 C. The asymmetric sulfur reaction mechanism, involving polysulfide intermediates, accounts for the high reaction kinetics at this temperature, simplifying thermal management. The battery shows a high capacity of 931 mAh g⁻¹ with low voltage hysteresis and excellent high-rate cycling stability. The quaternary melt electrolyte, with a melting point of -80°C, enables fast reaction kinetics and high cycling stability. The battery's performance is attributed to the presence of high-order Al-Cl clusters, which lower the Al³+ desolvation barrier. The nitrogen-doped carbon host is chemically compatible with the electrolyte and accelerates sulfur conversion. The battery demonstrates excellent rate capability and long-term cycling stability, with a discharge capacity of 542 mAh g⁻¹ and 85.4% capacity retention over 1400 cycles at 1 C. The asymmetric sulfur reaction mechanism, involving aluminum polysulfides, is crucial for the battery's rapid-charging capability. The study highlights the potential of sustainable Al-S batteries for both static and mobile energy storage with intrinsic safety and cost-effectiveness.A rapid-charging aluminium-sulfur battery operating at 85°C with a quaternary molten salt electrolyte is reported. The electrolyte, a quaternary alkali chloroaluminate melt, facilitates fast Al³+ desolvation due to abundant high-order Al-Cl clusters and a low melting point. A nitrogen-functionalized porous carbon cathode mediates the sulfur reaction, enabling rapid-charging capability and excellent cycling stability with 85.4% capacity retention over 1400 cycles at 1 C. The asymmetric sulfur reaction mechanism, involving polysulfide intermediates, accounts for the high reaction kinetics at this temperature, simplifying thermal management. The battery shows a high capacity of 931 mAh g⁻¹ with low voltage hysteresis and excellent high-rate cycling stability. The quaternary melt electrolyte, with a melting point of -80°C, enables fast reaction kinetics and high cycling stability. The battery's performance is attributed to the presence of high-order Al-Cl clusters, which lower the Al³+ desolvation barrier. The nitrogen-doped carbon host is chemically compatible with the electrolyte and accelerates sulfur conversion. The battery demonstrates excellent rate capability and long-term cycling stability, with a discharge capacity of 542 mAh g⁻¹ and 85.4% capacity retention over 1400 cycles at 1 C. The asymmetric sulfur reaction mechanism, involving aluminum polysulfides, is crucial for the battery's rapid-charging capability. The study highlights the potential of sustainable Al-S batteries for both static and mobile energy storage with intrinsic safety and cost-effectiveness.