Geopolymer recycled aggregate concrete (GRAC) was prepared by replacing cement with geopolymer and natural aggregate with waste concrete. The effect of the water-glass module on the mechanical properties of GRAC was studied. It was found that water-glass has a double-layer structure. The low module water-glass leads to a thicker diffusion layer and more Na⁺ and OH⁻ in the solution, which activates more CaO, SiO₂, and Al₂O₃ in the raw material, and improves the strength of GRAC. Moreover, two kinds of gel structures, namely layered C-A-S-H (calcium silicate hydrate) and networked N-A-S-H (zeolite), were found in the products of geopolymer. As the water-glass module changed, the phase of zeolite changed significantly, whereas the calcium silicate hydrate did not change, indicating that the decrease in the water-glass module contributes to the formation of more N-A-S-H gel. The compressive strengths of GRAC with the sizes of 200, 150, and 100 mm³ were in line with Bazant’s size effect theoretical curve. Through the segmented fitting method, the relationship of the size conversion coefficient of GRAC (α), the critical strength (f_cr), the critical dimension (D_cr), and the water-glass module (ε) were determined. It was found that ε = 1.5 is the segmented point of the three equations. The elastic modulus and peak stress of GRAC are inversely proportional to the water-glass module, and the peak strain is proportional to the water-glass module, indicating that by reducing the water-glass module, the strength of GRAC can be improved, but the brittleness is increased. The constitutive equation of GRAC with only the water-glass module as a variable was also established. It was found that the polynomial mathematical model and rational fraction mathematical model are optimal for the rising-stage and falling-stage, respectively, and the relationship between the parameters of the rising-stage (a) and the falling-stage (b), and the water-glass module, is given.

Alkali-activated binders (AABs) represent eco-friendly alternatives to ordinary Portland cement. Nevertheless, the synergistic influences of calcium dosage and aluminosilicate stoichiometry on phase assemblage, gel nanostructure, and mechanical properties have not been fully elucidated. Herein, AAB samples with graded CaO contents were fabricated, and the co-regulatory mechanisms of CaO dosage and Si/Al molar ratio on compressive strength and microstructural evolution were systematically explored through compressive strength tests, XRD, TG-DTG, FTIR, and SEM-EDS. In addition, pure reference C-S-H and N-A-S-H gels were synthesized by using the sol–gel method for comparison with AAB pastes. The results reveal that CaO dosage acts as the primary parameter dictating gel phase transition and strength level, categorizing the prepared AABs into three distinct zones: low-calcium region (CaO < 10 wt.%), medium-calcium region (10–20 wt.%), and high-calcium region (CaO > 20 wt.%). Combined grey relational and partial correlation analyses clarify the collinearity-induced false correlations and reveal the stage-dependent independent effects of oxide molar ratios on AABs’ compressive strength. Low-calcium AAB matrices are dominated by N-A-S-H gel networks coexisting with abundant low-strength zeolite crystals, which deteriorate thermal stability and retard strength gain. Increasing CaO content triggers a progressive phase transformation from N-A-S-H gel to high-strength C-(A)-S-H gel. Abundant Ca-rich chabazite and C-S-H gel form in high-calcium systems, which fill internal pores and microcracks and greatly enhance matrix densification and thermal resistance. This work clarifies the multiscale regulatory mechanism of calcium species over gel polycondensation, crystalline phase development, and mechanical performance of AABs, offering fundamental theoretical guidance for the customized design and property optimization of high-strength alkali-activated binders.