The paper focuses on the acid-free hydrothermal process for the synthesis of bioactive glass. The new method avoids the use of harmful acid catalysts, which are usually used in the sol-gel process. On the other hand, the processing time was reduced compared with the sol-gel method. A well-known ternary bioactive glass 58SiO2-33CaO-9P2O5 (wt%), which has been widely synthesized through the sol-gel method, was selected to apply to this new process. Thermal behavior, textural property, phase composition, morphology, and ionic exchange were investigated by thermal analysis, N2 adsorption/desorption, XRD, FTIR, SEM, and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis. The bioactivity and biocompatibility of synthetic bioactive glass were evaluated by in vitro experiments with a simulated body fluid (SBF) solution and cell culture medium. The obtained results confirmed that the acid-free hydrothermal process is one of the ideal methods for preparing ternary bioactive glass.