The purpose of this work was to propose and evaluate a new composition for a bioactive glass-ceramic starting from the well-known 45S5 commercial product. Thus, we developed a modified version, including MgO, an oxide that turned out to induce superior mechanical properties and improved biological response. This had the following molar percentages: 46.1% SiO2, 2.6% P2O5, 16.9% CaO, 10.0% MgO, and 24.4% Na2O. The precursor alkoxides and nitrates were processed by a standard sol-gel technique, resulting in a glass-ceramic target, suitable for laser ablation experiments. Combeite (Na2Ca2Si3O9) was identified as a main crystalline phase within the calcined sol-gel powder, as well as in the case of the target sintered at 900 °C. The thin films were deposited on silicon substrates, at room temperature or 300 °C, being subsequently characterized from the material point of view, as well as in terms of bioactivity in simulated conditions and biocompatibility in relation to human fibroblast BJ cells. The investigations revealed the deposition of nanostructured glassy layers with a low proportion of crystalline domains; it was shown that a higher substrate temperature promoted the formation of surfaces with less irregularities, as a consequence of material arrangement into a shell with better morphological homogeneity. The complex elemental composition of the target was successfully transferred to the coatings, which ensured pronounced mineralization and a stimulating environment for the cell cultures. Thereby, both samples were covered with a thick layer of apatite after immersion in simulated body fluid for 28 days, and the one processed at room temperature was qualified to be the best in relation to the cells.