[structure: see text] The neutral receptor N,N'-bis[3,5-di[(1-pyrenylmethyl)carbamoyl]benzyl] pyridine-2,6-dicarbamide (2) provides a pseudo-tetrahedron cleft and multiple hydrogen bondings to form a 1:1 complex with phosphate ion in a highly selective manner, by comparison with other anions (F(-), Cl(-), Br(-), SCN(-), AcO(-), NO(3)(-), ClO(4)(-), and HSO(4)(-)). The binding strength can be inferred from the emission intensity ratio of the pyrene monomer (lambda(max) 377 nm) to the excimer (lambda(max) 477 nm). Fluorescence titration, X-ray analysis, and NMR studies support a proposed complexation model.