Brillouin scattering has been used to study the elastic properties of alkaline-calcium silica hydrogels synthesized from the precipitation of sodium silicate solution with calcium hydroxide. To the best of our knowledge, this is the first determination of the bulk elastic moduli for this type of alkaline-calcium silica hydrogel, also referred to as the alkali-silica reaction (ASR) gel. The measured bulk moduli for the alkaline-calcium silica hydrogels were found to be between 4 and 8 GPa for the gel containing 0.08 M Ca(OH)2 and between 10 and 25 GPa for the gel containing 0.8 M Ca(OH)2, increasing with increasing pressure. Fourier transform infrared measurements were made to correlate the moduli to the silica speciation and network formation within the gels as a function of Ca(OH)2 content. Significantly, for the concentrations considered, both the interconnection of the silica species and the bulk modulus increased with increasing Ca(OH)2 content. On this basis, Brillouin scattering was confirmed to be a useful method for distinguishing between the bulk moduli of alkaline-calcium silica hydrogels in terms of chemical composition. The potential for further characterization of ASR gels as a function of composition and water content by this technique is highly promising.