(1) Background: valuation of the bioactivity and cytocompatibility of P2O5-free and CeO2 doped glasses. (2) Methods: all glasses are based on the Kokubo (K) composition and prepared by a melting method. Doped glassed, K1.2, K3.6 and K5.3 contain 1.2, 3.6, and 5.3 mol% of CeO2. Bioactivity and cytotoxicity tests were carried out in simulated body fluid (SBF) solution and murine osteocyte (MLO-Y4) cell lines, respectively. Leaching of ions concentration in SBF was determined by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). The surface of the glasses were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. (3) Results: P2O5-free cerium doped glasses are proactive according to European directives. Cerium increases durability and retards, but does not inhibit, (Ca10(PO4)6(OH)2, HA) formation at higher cerium amounts (K3.6 and K5.3); however, cell proliferation increases with the amount of cerium especially evident for K5.3. (4) Conclusions: These results enforce the use of P2O5-free cerium doped bioactive glasses as a new class of biomaterials.