The development of effective bone substitutes remains a central goal in regenerative medicine. In this study, lithium-modified bioglass-ceramics based on the 47.5S5 silicate oxide system were synthesized using the sol–gel method, followed by calcination and axial pressing to form cylindrical samples. These materials were sintered at 700 and 800 °C and subsequently examined to evaluate their structural, mechanical, and biological performance. Structural and microstructural analyses confirmed the presence of crystalline phases such as combeite (Na₆Ca₃Si₆O₁₈), NaLiSiO₄, Li₂SiO₃, and calcium silicates, indicating the successful incorporation of lithium within the glass-ceramic network. The bioceramics exhibited improved densification, deformability, and compressive strength with increasing sintering temperature. In vitro degradation in simulated body fluid revealed a consistent increase in mass loss with higher lithium content, suggesting enhanced resorbability linked to lithium oxide. Antibacterial testing indicated moderate antimicrobial activity, with slightly better results observed at higher sintering temperatures. Cell viability assays further supported the materials cytocompatibility. Taken together, these findings suggest that lithium substitution contributes positively to both mechanical robustness and biological behaviour, positioning these ceramics as promising bioresorbable bone substitutes with controlled degradation, suitable for bone tissue engineering where durability, bioactivity, and antimicrobial function are required.