An evaluation of the CaO-SiO₂ system has been made using a newly developed model, a two-sublattice model for ionic solutions. Two alternatives were tested. In the first one, three anions were assumed, O⁻², SiO₄ ⁻⁴, and SiO₃ ⁻². In the second one, SiO₃ ⁻² was omitted. A set of parameter values describing the Gibbs energy of the liquid phase and solid phases was fixed for each alternative by a computer-operated optimization procedure called PARROT. Satisfactory assessments were achieved over the whole phase diagram range with both alternatives. The main difference between them occurs at the monotectic point. A comparison between calculated properties and experimental data is given.