Zirconolite wasteforms were designed for the co-immobilisation of CeO2 (as a PuO2 surrogate) and metallic iron, chromium, and aluminum, simulating contaminated FeCrAl alloy cladding. Zirconolite ceramics with the target composition Ca(1-3.87x)Ce3.87xZrTi(2-7.73x)Fe5.73xCrxAlxO7 (x = 0–0.11), were synthesised via solid state reaction sintering at 1400 °C. Phase and microstructural evolution were investigated to ensure the oxidation of the metals, formation of zirconolite phase and densification of the final ceramics. It was found that both oxidation and solid-state reaction could be accomplished by processing at 900 °C and 1400 °C under ambient atmosphere, accompanied by the overall yield of zirconolite in the range 92.4–94.0 wt % between x = 0.01–0.07 f.u., with a dense microstructure observed. Polytype transitions from zirconolite-2M to -3T were evidenced, where the solubility limit was reached at substitution level of x = 0.11 and precipitation of CeO2 was apparent. XPS analysis confirmed that an elevation in dopant concentration resulted in the partial reduction of Ce4+ to Ce3+, whereas Fe, Cr and Al metals were oxidised to the trivalent state. This study demonstrated the feasibility for designing advanced ceramic wasteforms for the co-immobilisation of actinides and metallic cladding residues.