Two structurally simple and easily synthesized luminescent anion receptors featured with an amide-type anion binding site and rhenium(1) tricarbonyl pyridine signaling units have been developed, and they display outstanding sensitivity and selectivity toward a variety of anionic species. These complexes are highly emissive, in solution. Upon anion binding, the emission intensity was significantly quenched. The sensitivities of these complexes are so high that the emission intensity can be effectively quenched by as much as 10% even in the presence of only 10(-8) M cyanide or fluoride anions. The ability of formation of intramolecular hydrogen bonding between the amide protons and central pyridine is believed to be responsible for the observed high selectivity.