The heat of hydration, mechanical properties, pozzolanic activity, and microscopic characteristics of cement pastes incorporating co-combusted fly ash (CCFA) were investigated, and the disparities between the CCFA/cement system and the coal fly ash (CFA) binding system were also compared. The results indicate a decrease in the heat of hydration for both CFA and CCFA samples, with a more pronounced trend observed as the fly ash content increased from 10% to 30%. The distinction in the early hydration between CFA and CCFA samples primarily manifested in the rate of heat release, potentially correlated with variations in the active Al2O3 content in the fly ash. Neither CFA nor CCFA samples exhibited significant cementitious activity at 3 days, functioning solely as inert fillers in the cement paste. By 3 and 28 days, the mechanical properties of both CFA and CCFA samples were inferior to those of pure cement paste. However, by 180 days of hydration, the compressive strength of CCFA-blended mortar notably increased, with the highest strength observed in the 10% CCFA-blended sample. Both CFA and CCFA samples produced the secondary hydration product C-A-S-H and demonstrated comparable consumption of calcium hydroxide (CH). These findings underscore the potential of CCFA as a supplementary cementitious material (SCM) and lay a foundation for its widespread adoption.