Glass-ceramics of eutectic composition in the wollastonite [W, CaO⋅SiO2]- tricalcium phosphate [TCP, β-Ca3(PO4)2] binary system were synthesized by using the glass-crystallization method. The parent glass was crystalized at 800-1300 °C for 0.5-5 h. The in vitro bioactivity of the synthesized glass-ceramics was tested in Kokubo’s Simulated Body Fluid (SBF) for 7-21 days, at pH = 7.4 and 37 °C. All materials were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM/EDS). The results showed that metastable Apatite phase [Ap, Ca10(PO4)6O], plus W and TCP phases expected according to the binary phase diagram, were formed. Ap was the first phase formed at 900 °C/0.5 h, which was followed by formation of W phase at 900 °C/2 h and of TCP phase at 1200 °C/0.5 h. The relative proportion of the formed crystalline phases was a function of heat treatment temperature and time. A eutectic microstructure was obtained for the materials heat-treated at 1300 °C for 2 or 5 h. All glass-ceramics showed the formation of a hydroxyapatite (HAp)-like layer during the in vitro bioactivity tests. After 21 days of soaking in SBF, the samples treated at 1300 °C/5 h showed a behavior similar to that typically shown by Bioeutectic® material, while the materials heat-treated at lower temperatures tended to form denser HAp-like layers, with similar thicknesses but with higher Ca/P molar ratios.