A model describing the distribution of silicate sites in concentrated alkali metal silicate solutions used in the synthesis of geopolymeric gels is presented. The model is based on a free energy 14 minimization algorithm, using free energy of formation data obtained from the literature. A simplified form of the Pitzer method (Pitzer, K. S. J. Phys. Chem. 1973, 77, 26) is used to calculate activity coefficients, with interaction parameters calculated from known values for ions of similar size and charge type. Ion pairing effects are incorporated into the model formulation by a simple approximation, whereby larger cyclic or cagelike ions form strong ion pairs with dissolved alkali metal cations, and smaller monomeric (Q(0)) or end-group (Q(1)) sites pair less strongly with the cations. The model is able to describe accurately the speciation data obtained from a systematic Si-29 NMR investigation of sodium, potassium, and mixed (1:1) sodium/potassium silicate solutions. The model is also tested against a large data set from the literature on sodium silicate solutions with a wide range of compositions. The model provides understanding of the speciation of silicate solutions and a basis for further understanding and modeling of the geopolymerization process.