Owing to the depletion of bauxite and increasing demand for alumina, calcination methods for extracting alumina from coal fly ash (CFA) were developed. However, these methods have disadvantages such as the need for high temperatures and the emission of toxic gases. Hence, in this study, Al2O3 was extracted from CFA via low-temperature potassium bisulfate calcination technology. Effects of the potassium bisulfate amount, calcination temperature, and calcination time on the alumina extraction efficiency were investigated using X-ray diffraction, thermal gravimetry, scanning electron microscopy, differential scanning calorimetry, and energy-dispersive spectroscopy. It was found that this technique could recover alumina efficiently, and potassium bisulfate significantly contributed to the degradation of mullite and corundum phases. Al2O3 in CFA was converted into soluble K3Al(SO4)(3). With a KHSO4/Al2O3 molar ratio of 7:1, calcining temperature of 230 degrees C, and calcining time of 3 h, the alumina extraction efficiency reached a maximum of 92.8%. The Avrami-Erofeev equation showed the best fit with the kinetic data for the low-temperature calcination of CFA with KHSO4. The activation energy was 28.36 kJ/mol.