As a key component of nuclear fuel, actinide element purity is a critical technical parameter throughout the nuclear fuel cycle, from initial mining and purification to subsequent recovery processes. At the same time, rhenium (Re), which play an important role in the field of defense and aerospace, is very scarce, and the extraction and enrichment of Re from solution is currently considered to be an effective means. In addition, Re is considered to be a model of radionuclide technetium-99 (99Tc), and the adsorption process of Re provides a reference for the adsorption and separation of Tc elements, which shares a similar mechanism. In this study, supramolecular pseudorotaxane ligands with large size had been selected for the co-crystallization separation of actinides and ReO4− in solution. Under hydrothermal conditions, a flexible guest molecule ([LEt]Br2) with a dipyridinium skeleton was assembled with a cucurbituril macrocycle (CB[7]) to form a supramolecular pseudorotaxane ligand (L@CB[7]).This ligand was then co-crystallized with uranyl ions and ReO4− in solution, resulting in a one-dimensional chain crystal with infinite extension, where ReO4− served as counterion. The findings indicate that the carboxyl group of dipyridinium salts can be complexed with uranyl ions in solution to form a cationic skeleton structure capable of trapping ReO4− ions. The large size supramolecular pseudorotaxane ligand shows promise for the co-crystallization separation of uranium and TcO4− from high-level waste liquid, potentially enabling the efficient extraction of high-purity radionuclides from complex environments and facilitating the enrichment, separation, and reuse of uranium and technetium elements.