In response to the environmental implications of the massive quantities of excavation soil generated by global urbanization and infrastructure development, recent research efforts have explored the repurposing of calcined excavation soils as sustainable supplementary cementitious materials (SCMs). As it is still at an early stage, current research lacks systematic analysis across diverse soil deposits regarding their reactivity and mechanical properties within cementitious binders, despite recognized geographical variability in kaolinite content. Through comprehensive experimentation with soils sourced from four major southern Chinese cities, this study presents a pioneering assessment of the compressive strength, pozzolanic reactivity (X-ray diffraction, Fourier-transform infrared spectroscopy, solid-state nuclear magnetic resonance), and microstructural development (mercury intrusion porosimetry, scanning electron microscopy) of mortars modified by various calcined excavation soils (up to 28 days curing). The experimental data suggest that soils with a kaolinite content above 53.39% produce mortars of equal or superior quality to plain cement mixes, primarily due to their refined pore structures, microstructural densification, and enhanced hydration reactions. The findings highlight kaolinite—specifically, aluminum content—as the principal indicator of excavation soil viability for SCM application, suggesting a promising avenue for sustainable construction practices.