Supramolecular gels with hierarchical order and complexity have been assembled. The gels contain well-defined Ag4L2 luminescent supramolecular cages as cores, which are cross-linked via Ag-P coordination bonding. The resulting gels are highly luminescent and exhibit rich stimuli-responsive behaviors toward mechanical and chemical (nitroexplosive and anions) stimuli. The gels could be transformed to highly luminescent crystal materials upon addition of halogen anions, in which only traces of lumiphor are accommodated in a host crystal matrix.