A new approach to anion sensing that involves excimer disaggregation induced emission (EDIE) is reported. It involves the anion-mediated disaggregation of the excimer formed from a cationic macrocycle. This leads to an increase in the observed fluorescence intensity. The macrocycle in question, cyclo[1] N2, N6-dimethyl- N2, N6-bis(6-(1 H-imidazolium-1-yl)pyridin-2-yl)pyridine-2,6-diamine[1]1,4-dimethylbenzene (12+; prepared as its PF6- salt), is obtained in ca. 70% yield via a simple cyclization. X-ray diffraction analyses of single crystals revealed that, as prepared, this macrocycle exists in a supramolecular polymeric form in the solid state. Macrocycle 12+ is weakly fluorescent in acetonitrile. The emission intensity is concentration dependent, with the maximum intensity being observed at [12+] ≈ 0.020 mM. This finding is ascribed to formation of an excimer, followed possibly by higher order aggregates as the concentration of 12+ is increased. Addition of tetrabutylammonium pyrophosphate (HP2O73-) to 12+ (0.020 mM in acetonitrile) produces a ca. 200-fold enhancement in the emission intensity (λex = 334 nm; λem = 390-650 nm). These findings are rationalized in terms of the HP2O73- serving to break up essentially non-fluorescent excited-state dimers of 12+ through formation of a highly fluorescent anion-bound monomeric complex, 12+·HP2O73-. A turn-on in the fluorescence intensity is also seen for H2PO4- and, to a lesser extent, HCO3-. Little (HSO4-, NO3-) or essentially no (N3-, SCN-, F-, Cl-, Br- and I-) response is seen for other anions. Solid-state structural analysis of single crystals obtained after treating 12+ with HP2O73- in the presence of water revealed a salt form wherein a H2P2O72- anion sits above the cone-like macrocycle.