The growing use of blends of low- and high-calcium solid precursors in combination with different alkaline activators requires simple, efficient, and accurate experimental means to characterize their behavior, particularly during the liquid-to-solid transition (setting) at early material ages. This research investigates slag-fly ash systems mixed at different solution-to-binder (s/b) ratios with sodium silicate/sodium hydroxide-based activator solutions of varying concentrations. Therefore, continuous non-destructive tests—namely ultrasonic pulse velocity (UPV) measurements and isothermal calorimetry tests—are combined with classical slump flow, Vicat, and uniaxial compressive strength tests. The experimental results highlight that high alkali and silica contents and a low s/b ratio benefit the early-age hydration, lead to a faster setting, and improve the early-age strength. The loss of workability, determined from the time when the slump flow becomes negligible, correlates well with ultrasonic P-wave velocity evolutions. This is, however, not the case for Vicat or calorimetry tests.