Glasses belonging to the CaO-ZrO2-SiO2 ternary system were prepared by melting raw materials at 1600 degreesC. Several properties of the glassy materials, such as density and thermal behavior, were experimentally determined, and the results were interpreted by comparison with the structural information derived from molecular dynamics simulations and from Si-29-MAS NMR. A detailed analysis of the short- and intermediate-range structure was performed to define the role played by the different atoms present in the glass formulation and to correlate the structural modifications to the macroscopic properties of this class of glasses.