A series of supramolecular transformation cascades are presented here, employing ligand exchange reactions, concentration-dependent Borromean ring (BR) linking and unlinking, and inverse electron-demand Diels Alder (IEDDA) reactions. The new family of template-free, tetrazine-edged BRs are constructed by using ligand exchange reactions, and their concentration dependent linking and unlinking reactions have been observed. Moreover, Borromean precursors have been demonstrated to further undergo supramolecular structural transformations induced by rapid and efficient IEDDA reactions to afford corresponding post-assembly modified architectures. Remarkably, subtle steric increases of the pyridazine fragments obtained by IEDDA reactions is regarded to induce controlled topological transformations in the cascade, unlinking the Borromean structures by using electron-rich dienophiles as triggering signals.