Supramolecular assembly is shown to provide control over excited-state chloride release. Two dicationic chromophores were designed with a ligand that recognizes halide ions in CH2Cl2 and a luminescent excited state whose dipole was directed toward, 1(2+), or away, 2(2+), from an associated chloride ion. The dipole orientation had little influence on the ground-state equilibrium constant, K-eq similar to 4 X 10(6) M-1, but induced a profound change in the excited-state equilibrium. Light excitation of [1(2+),Cl-](+) resulted in time-dependent shifts in the photoluminescence spectra with the appearance of biexponential kinetics consistent with the photorelease of Cl-. Remarkably, the excited-state equilibrium constant was lowered by a factor of 20 and resulted in nearly 45% dissociation of chloride. In contrast, light excitation of [2(2+),Cl-](+) revealed a 45-fold increase in the excited-state equilibrium constant. The data show that rational design and supramolecular assembly enables the detection and photorelease of chloride ions with the potential for future applications in biology and chemistry.