A novel method was developed for extracting alumina (Al₂O₃) from fly ash using an ammonium hydrogen sulfate (NH₄HSO₄) roasting process, and the thermodynamics and kinetics of this method were investigated. The thermodynamic results were verified experimentally. Thermodynamic calculations show that mullite present in the fly ash can react with NH₄HSO₄ in the 298–723 K range. Process optimization reveals that the extraction rate can reach up to 90.95% when the fly ash reacts with NH₄HSO₄ at a 1:8 mole ratio of Al₂O₃/NH₄HSO₄ at 673 K for 60 min. Kinetic analysis indicates that the NH₄HSO₄ roasting process follows the shrinking unreacted core model, and inner diffusion through the product layer is the rate-controlling step. The activation energy is calculated to be 16.627 kJ/mol; and the kinetic equation can be expressed as 1 − (2/3)α − (1 − α)^2/3 = 0.0374t exp[−16627/(RT)], where α is the extraction rate and t is the roasting temperature.