Zirconolite (CaZrTi2O7) based glass-ceramics designed for the specific immobilization of plutonium wastes or minor actinides (Np, Am, Cm) from high level radioactive wastes were investigated. To reach an efficient double containment, actinides must be preferentially located in the crystalline phase, which is homogeneously dispersed in a calcium aluminosilicate residual glass. Several heat treatments (between 950° and 1350°C) of a parent glass belonging to the SiO2-Al2O3-CaO system and containing TiO2 and ZrO2 were performed to prepare glass-ceramics. Trivalent minor actinides were simulated introducing Nd2O3 in the glass composition. Electron microscopy, X-ray diffraction (XRD) and thermal analysis have shown that devitrification processes in the bulk and on glass surface are different. They lead to the crystallization of zirconolite in the bulk and to a mixture of titanite (CaTiSiO5) and anorthite (CaAl2Si2O8) near the surface. For heat treatment temperatures greater than or equal to 1250°C, baddeleyite (m-ZrO2) crystals form at the expense of zirconolite in the bulk of glass-ceramics. XRD indicates that the order in zirconolite Ca/Zr planes increases with heating temperature. At the same time, extended defects density decreases.