Plutonium recovery is inevitable from plutonium bearing alumina crucibles generated over the years as part of carbon analysis during chemical quality control of nuclear fuels. This is a challenging task owing to the complex nature of matrix. The first stage of methodology development of plutonium recovery involved usage of CeO₂ bearing crucibles. Cerium distribution in alumina crucible was investigated by examination of surface morphology. Various aqueous recovery routes were tested initially with CeO₂ bearing crucibles and 4 M HF–8 M HNO₃–NH₄NO₃ was found to be most promising (60% recovery). The same route yielded 90% plutonium recovery from alumina crucibles.