Stimuli-induced structural transformation of supramolecular cages has drawn increasing attention because of their sensitive feature to external variations as model systems to simulate biological processes. However, combining structural transformation and useful functions has remained a difficult task. This study reports the solvato-controlled selfassembly of two unique topologies with different emission characteristics, a water-soluble Ag 8 L 4 cage (A) and an Ag 4 L 2 cage (B), produced from the same sulfonate-pendant tetraphenylethene (TPE) bridged tetrakis-(1,2,4-triazolium) ligand. Both cages show interesting solvent-responsive reversible structural transformation, and the change of fluorescence signals can efficiently track the process. Additionally, watersoluble cage A exhibits unique properties in thermochromism, thiol amino acid sensing, and subcellular imaging in aqueous media.