A novel self-assembly system has been developed, in which Ag₆L₄ cages can not only effectively assemble into a polycatenane containing multiple mechanical bonds in their supersaturated (MeOH–CHCl₃) solution in a kinetically-controlled way, but can also be directly linked into a highly ordered polycage in the unsaturated solution through a thermodynamically-controlled assembly process. Moreover, the newly-constructed multiple mechanical bonds can also be opened and transformed into metal–metal interactions through reconstruction of the kinetically-controlled product into the thermodynamically-controlled product in the (MeOH–CHCl₃) system, while the more strongly polarised DMSO solution can only open these multiple mechanical bonds.