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 NaO with MgO on the electrical, biosolubility, and thermal properties of the target glass 10NaO-60PO-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 × 10 to 4.21 × 10 S cm after complete substitution of MgO for NaO. All samples had a similar activation energy of the DC conduction process ~1.27 eV. Conduction mechanisms were found to be due to hop of ions: Na, Mg and probable H. FTIR analysis showed that, as the Mg content increased, the Q unit (PO) shifted towards higher wavenumbers. The proportion of Q unit (PO) decreased in the glass structure. This confirmed that the replacement of Na by Mg 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 NaO-CaO-PO 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 NaO by MgO.