Circulating fluidized bed combustion (CFBC) ash, a byproduct typically generated from coal-fired CFBC power plant boilers, contains high content of free lime and anhydrite. Due to its chemical composition, CFBC ash exhibits self-cementing properties; however, its performance is limited. One approach to enhancing the self-cementing properties of CFBC ash is through the incorporation of mineral admixtures such as gypsum. This study investigated the influence of desulfurization gypsum (DG) on the self-cementing behavior of CFBC ash. To this end, paste and mortar specimens were prepared and evaluated for their hydration and mechanical characteristics. The hydration behavior was analyzed using isothermal calorimetry, thermogravimetric analysis (TGA), setting time measurements, and X-ray diffraction (XRD) analysis. Mechanical properties were assessed by measuring the compressive strength at various curing ages. Additionally, changes in microstructure were examined by evaluating the pore size distribution through mercury intrusion porosimetry (MIP). The experimental results indicate that the appropriate incorporation of DG enhances the hydraulic reactivity of CFBC ash and significantly improves the compressive strength.