‘Fused/cast Al2O3–ZrO2–SiO2 (FC-AZS)’ is being considered as ‘glass contact refractory’ within ceramic melters, to be used for nuclear waste immobilization. Microstructural analyses reveal random distributions of baddeleyite (ZrO2) within aluminosilicate (Al2SiO5) matrix. 27Al and 29Si NMR data suggest that within aluminosilicate matrix Al occurs in both 4- and 6-fold co-ordinations whereas Si prefers a 4-fold environment. Polydispersity of pores has been studied with small-angle neutron scattering (SANS) technique. Corrosion rates of FC-AZS within 6 M HNO3, simulated wastes (500 h exposure), and borosilicate melt (975 °C, 800 h exposure) are found to be 0.38 × 103 μmy−1, 0.13 × 103 μmy−1 and 4.75 × 103 μmy−1 respectively. A comparison of chemical interaction data clearly suggests that FC-AZS exhibits better chemical durability than AZC refractory (Al2O3–ZrO2–Cr2O3, also used for similar purpose). Thermal cycling studies indicate that FC-AZS retains structural integrity (including compressive strength and density) even up to 20 cycles.