Despite their global abundance, heterogenous clays are often excluded from SCM applications, due to their limited pozzolanicity. This study investigates hydration evolution, particularly aluminum uptake pathways, in statistically designed cement blends incorporating thermo-mechanochemically activated low-kaolinite clays. Despite kaolinite contents below 40%, a 30% binary blend achieved 110% and 125% of OPC strength at 7 and 56 days, respectively, while reducing total porosity by 42% at 56 days. 29Si NMR indicated an increase in silicate chain length in C-(A)-S-H, correlating with pore structure refinement and strength gain in 56 days of hydration. 27Al NMR revealed a preferential incorporation of aluminum into C-(A)-S-H rather than AFm phases. This behavior is attributed to the lower alumina availability in the system compared to LC3 blends, suggesting that in such environments, C-(A)-S-H becomes the dominant host phase for aluminum. This incorporation pathway reduces the Al availability for carbonate-AFm formation, limiting the synergy typically observed in LC3 systems with added limestone.