This study addresses a key unresolved question in alkali-activated materials: how externally supplied calcium from limestone influences calcium-induced hybrid gel formation under NaOH-only activation in precursor systems with different initial calcium availability. Unlike previous studies focusing mainly on strength development or using combined alkaline activators, this work establishes a composition-dependent mechanistic framework linking calcium availability, reaction kinetics, microstructural evolution, and engineering performance. Limestone additions (5–10 wt.%) were incorporated into fly ash (FA0) and slag–fly ash (FAS0) binders activated with 8 M NaOH and cured at 65 °C. In the low-calcium fly ash system, compressive strength increased from 29 to 38 MPa (≈30%), with nearly 90% of the ultimate strength achieved within the first 24 h. In contrast, slag-containing binders exhibited strength variations below 5%, indicating limited additional benefit once sufficient calcium was intrinsically available. Integrated characterization (SEM/EDS, XRD, FTIR, isothermal calorimetry, and TGA–DSC) consistently supports the progressive transformation from predominantly N–A–S–H gel toward hybrid calcium-containing binding environments. The combined evidence suggests that localized calcium availability associated with limestone accelerates hybrid gel formation and microstructural densification rather than acting solely as an inert carbonate filler. These findings provide practical guidelines for designing low-carbon hybrid alkali-activated binders with tailored reaction kinetics, optimized engineering performance, and improved material efficiency.