The process of alkali activation of fly ash and metakaolin is examined in the view of micromechanics. Elasticity is predicted via semi-analytical homogenization methods, using a combination of intrinsic elastic properties obtained from nanoindentation, evolving volume fractions and percolation theory. A new quantitative model for volume fraction is formulated, distinguishing the evolution of unreacted aluminosilicate material, solid gel particles of N-A-S-H gel, and open porosity, which is partially filled with the activator. The stiffening of N-A-S-H gel is modeled by increasing the fraction of solid gel particles. Their packing density and intrinsic elasticity differ in N-A-S-H gels synthesized from both activated materials. Percolation theory helps to address the quasi-solid transition at early ages and explains a long setting time and the beneficial effect of thermal curing. The low ability of N-A-S-H gel to bind water chemically explains the high porosity of Ca-deficient activated materials. Micromechanical analysis matches well the elastic experimental data during the activation and elucidates important stages in the formation of the microstructure.