This study demonstrates the ability of ammonium uranyl peroxide nanoclusters U32R-NH4 to undergo exchange in between NH4(+) and trivalent (Nd(3+)) or tetravalent (Th(4+)) cations in the solid state. It paves the way for new promising routes for the synthesis of mixed uranyl peroxides. The exchange ability may also be considered for solution decontamination and synthesis of new mixed actinide-oxide precursors. Both of these applications could be used in the nuclear industry.