Boron oxide doped glasses with a composition of (80–x)NaPO3–xB2O3–5CaF2–15MgO with x = 20, 25, 30, 35 and 40 mol% were synthesized through the melt quench technique. The density of prepared glasses was found to decrease, while the molar volume increased as the B2O3 content varied from 20 to 40 mol%. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) studies were performed to examine the amorphous nature and structural modifications of the glasses, respectively. Ultraviolet (UV) spectra in the wavelength range of 200–800 nm have been measured for the entire glass series. The UV–visible absorption spectra of the glasses exhibit a broad absorption band at approximately 220 nm. Using Tauc plots, the optical band gaps were determined from the optical absorption spectra. The refractive index and density of glasses were used to compute various other parameters such as ion concentration, polaron radius, internuclear distance, oxide polarizability and optical basicity values. The elastic parameters, including longitudinal modulus (L), shear modulus (G), bulk modulus (K), Young’s modulus (E) and Poisson’s ratio, were calculated using the Makishima and Mackenzie models. The glasses were immersed in a simulated body fluid (SBF) solution for 7 and 14 days to conduct in vitro bioactivity studies. The formation of apatite layers on the glass surfaces was evaluated using XRD and FTIR analyses.