Bioactive glasses have recently been extensively used to replace, regenerate, and repair hard tissues in the human body because of their ability to bond with living tissue. In this work, the effects of replacing Na₂O with MgO on the electrical, biosolubility, and thermal properties of the target glass 10Na₂O-60P₂O⁵-30CaO (in mol%) were investigated. The electrical properties of the glasses were studied with the impedance spectroscopy technique. At 473 K, DC conductivity values decreased from 4.21 x 10^-11 to 4.21 x 10^-12 S cm^-1 after complete substitution of MgO for Na₂O. All samples had a similar activation energy of the DC conduction process similar to 1.27 eV. Conduction mechanisms were found to be due to hop of ions: Na⁺, Mg²⁺ and probable H⁺. FTIR analysis showed that, as the Mg content increased, the Q² unit (PO₂^-) shifted towards higher wavenumbers. The proportion of Q³ unit (P₂O₅) decreased in the glass structure. This confirmed that the replacement of Na⁺ by Mg²⁺ was accompanied by concurrent polymerization of the calcium-phosphate glass network. The biosolubility test in the phosphate-buffered saline solution showed that the magnesium addition enhanced the biosolubility properties of Na₂O-CaO-P₂O₅ glasses by increasing their dissolution rate and supporting forming CaP-rich layers on the surface. The glass transition temperature increased, and thermal stability decreased substantially upon substitution of Na₂O by MgO.