Niobium doped biosolubility glasses in the Na–Ca–(Mg)–P–Si–O system were prepared by using an untypical two-step synthesis route. The parent glass was melted in air atmosphere at 1350 °C followed by re-melting the glass in Nb crucible with the addition of metallic Mg/Ca powder in the nitrogen atmosphere. The second melting step was carried out at 1450–1650 °C, using an induction furnace. The topography and structure of the obtained glasses were characterized by confocal microscopy, X-ray powder diffraction and infrared spectroscopic techniques. The chemical compositions were examined by energy-dispersive X-ray spectroscopy (EDS). The glasses were found to be of grayish color, X-ray amorphous and having network connectivity between ~ 2.5 and 2.7. The network connectivity of re-melted glasses was lower than the one of the parent glass. The glass structure consists of a highly disrupted silicate network of predominantly Q2 groups as well as isolated orthophosphate tetrahedra. The parent glass contains nanocrystallites consisted of apatitic PO₄³⁻ groups. The re-melted glasses contain non-apatitic or amorphous calcium phosphates. The obtained glass transition temperatures range from 530 to 568 °C and exhibit higher values for glassed doped with Ca metal. These glasses have improved thermal stability as compared to reference bioglasses. The biosolubility test in phosphate buffered saline solution (PBS) confirms that the glasses have biosolubility properties and HAp formation on the surfaces was observed.