In hybrid alkaline fly ash cements, a new generation of binders, hydration, is characterized by features found in both ordinary portland cement (OPC) hydration and the alkali activation of fly ash (AAFA). Hybrid alkaline fly ash cements typically have a high fly ash (70 wt % to 80 wt %) and low clinker (20 wt % to 30 wt %) content. The clinker component favors curing at ambient temperature. A hydration mechanism is proposed based on the authors’ research on these hybrid binders over the last five years. The mechanisms for OPC hydration and FA alkaline activation are summarized by way of reference. In hybrid systems, fly ash activity is visible at very early ages, when two types of gel are formed: C–S–H from the OPC and N–A–S–H from the fly ash. In their mutual presence, these gels tend to evolve, respectively, into C–A–S–H and (N,C)–A–S–H. The use of activators with different degrees of alkalinity has a direct impact on reaction kinetics but does not modify the main final products, a mixture of C–A–S–H and (N,C)–A–S–H gels. The proportion of each gel in the mix does, however, depend on the alkalinity generated in the medium.