Phosphate glasses are important materials in many fields. However, their usage can be limited due to water corrosion. Addition of Al 2 O 3 significantly improves the water resistance, and as such, the glass of superior water durability can be obtained. Thus, it may be considered as a matrix for waste immobilization. In the paper, thermal properties of 60P 2 O 5 -(40-x)Al 2 O 3 -xNa 2 O glasses are presented. The materials were investigated with the application of DSC/TG method and observations of shape change during heating in a heating microscope. Water durability studies are also presented. It was evidenced that glass of low Na 2 O content crystallizes during heating, which limits their application in waste vitrification. Nevertheless, the obtained glass-ceramic material is characterized by a superior water resistance. The water durability decreases with sodium content. The obtained results are discussed from a waste immobilization point of view, and the optimal glass composition containing 15 mol% of Na 2 O is indicated due to it low viscosity, melting temperature and very good water resistance.