The use of nuclear materials is increasing in energy production, medicine, and environmental sectors. Following this trend, the generation of radioactive wastes is also increasing in the whole production cycle and use of this kind of materials. Among these, the 137Cs radionuclide presents a potential risk to human health due to its half-life time (30,2 years), high-level activity (1 TBq) and easiness to contaminate rivers, soil, and air. The immobilization of 137Cs in solid matrices has been an available option researched by several countries. In this context a new glass composition based on aluminoborosilicate glass modified with niobium (Nb) was used for the immobilization of cesium through adding Cs-loaded zeolite. Homogeneous vitreous wasteforms were improved with the growth of Nb content in the compositions. All compositions were able to keep up to 5.9 wt% Cs2O, previously adsorbed by zeolite A, and the immobilization efficiency was around 53%. Their structural analyses by Raman revealed a depolymerized and complex network structure, due to the presence of several cations including Cs. In turn, Nb reflected positively on the chemical resistance and thermal properties, by changing the distribution of silicate species. The wasteforms presented good glass forming ability and thermal stability up to 520 °C. Through the thermal treatment for devitrification, Cs atoms were stabilized into the Pollucite phase (CsAlSi2O6). Besides that, the wasteforms, preferably the one containing 8.0 mol% Nb, showed low elemental releases and leaching rates for Cs (1 × 10−3 g m2.day−1), after the leaching experiments at 90 °C for 7 days in static conditions, verified by the neutron activation analysis (NAA).