The heat treatment conditions are a key factor in fabricating zirconolite ceramics and glass-ceramics following high-temperature melting. An oxide mixture melted at 1450°C and subsequently heat-treated at 1200°C yielded a glass-ceramic containing crystallized zirconolite–2M. The silica-enriched residual glass represented about 60-70 vol% of the total; the actinide surrogates (Nd, Ce)were equally distributed between the residual glass and the zirconolite crystals. Zirconolite ceramics obtained after melting an oxide mixture at 1600–1700°C consisted of zirconolite, perovskite and rutile. Rapid cooling rates (> 100°#x00B0;··min-1) were obtained by pouring the melt into ingot molds; the resulting zirconolite ceramics were characterized by crystals of zirconolite-2M ranging from 1 to no more than 20 μm. Slow cooling (< 25°C#x00B0;··min-1 produced ceramics with crystals several hundred micrometers long. Despite the microstructural differences, the chemical durability of the zirconolite ceramics was identical. The initial alteration rates r 0 were about two orders of magnitude lower than those measured for the residual aluminosilicate glass of the zirconolite glass-ceramics. Moreover, during long-term leach tests at high S/V ratios to obtain advanced degrees of reaction progress, the alteration rates of all the materials diminished by over 3 to 4 orders of magnitude below r 0.