Calcium is an essential component of osteogenesis and is often required for imparting significant bioactivity to synthetic bone substitutes and, in particular, silicate-based materials. However, the mechanism of calcium incorporation inside sol–gel silicates is poorly understood. In this work, we shed light on the determinant parameters for incorporation of calcium into acid–base-catalyzed sol–gel silicates at ambient temperature: increasing the pH above the isoelectric point of silicic acid and the nature of the calcium counterion in the calcium precursor are found to be the key. Based on our proposed reaction sequence, we were able to compare calcium precursors and select an ideal candidate compound for the synthesis of bioactive glasses (BG) and organic–inorganic hybrids at ambient temperature. Reproducible syntheses and gel times of SiO2–CaO BG were obtained using calcium hydroxide (CH), and we demonstrate its usability in the synthesis of promising BG–polycaprolactone hybrid scaffolds. BG and hybrids prepared with CH were able to form nanocrystalline nonstoichiometric apatite in simulated body fluid. The increased reliability of low-temperature syntheses associated with the use of a stable and inexpensive alkaline-earth precursor are major steps toward the translation of calcium silicate hybrids or other alkaline-earth silicates from bench to clinic.