Six kinds of naphthyl urea and thiourea podands were designed and synthesized. The interaction between these compounds and various guest anions are studied in molecular level via absorption, fluorescence and 1H NMR spectra. The experiments show that tri-podal urea or thiourea host can bind H2PO4-or HSO4-selectively and form a host-guest complex thus inducing a change in photophysical properties of host molecule. Through comparison between urea and thiourea compounds used as host molecules, the stability constants and stoichiometry of the complexes have been determined. The binding manner and possible structures of them have been proposed. The interaction between these compounds and various guestions are studied at molecular level via absorption, fluorescence and 1H NMR spectra. The experiments show that tri-podal urea or thiourea host can bind H2PO4 -or HSO4-selectively and form a host-guest complex thus inducing a change in photophysical properties of host molecule. Through comparison between urea and thiourea compounds used as host molecules, the stability constants and stoichiometry of the complexes have been determined. The binding manner and possible structures of them have been proposed.