A large amount of low-level radioactive concrete nuclear waste with contamination and activation will be generated when the nuclear facilities are decommissioned. Glass material has been used to immobilize kinds of radioactive wastes because of its wide incorporation to radioactive elements and excellent chemical durability, compared with traditional cement solidification. In this paper, the simulated structural concrete nuclear waste was treated by high temperature melting. The concrete was vitrified with the glass additive (~26% (mass fraction) SiO2, ~13% (mass fraction) B2O3 and ~6% (mass fraction) Na2O) at 1 300 ℃, and the chemical durability of thus resulted glass waste form meets the disposal requirements for low-level waste form. The volatilization behavior of the simulated nuclides at high temperature and their local structure in the glass were finally discussed. The results can provide the basic information to vitrify the concrete nuclear waste.