Anions　display　a　great　significant　role　in　the　environment　and　life　science.　The　design　and　synthesis　of　receptors　with　high　selective　recognition　anion　has　attracted　considerable　attention.　The　selective　identification　fluoride　anion　of　benzocoumarin-based　thiourea　receptors　4a~4e　were　obtained　starting　from　β-naphthol　by　a　multi-step　reaction.　Their　structures　were　characterized　by　1H　NMR,　13C　NMR,　IR　and　elemental　analysis.　The　interactions　between　receptors　4a~4e　and　anions　(F-,　AcO-,　C1-,　Br-,　I-,　HSO4-)　were　studied　by　optical　(UV-Vis　absorption　and　fluorescence)　and　1H　NMR　spectroscopy.　The　results　showed　that　the　receptors　with　anion　through　hydrogen　bonds　formed　stable　1:2　complexes,　which　leaded　to　the　change　spectroscopy　of　receptor　molecules.　Determination　of　the　combined　ratio　and　the　stability　constants　of　complexes　were　borne　out　receptor　molecules　with　high　alternative　recognition　F-　or　AcO-　anions　with　limit　of　detect　of　5.45　and　7.00　μg/L　and　the　effect　of　reaction　time　of　5　min　and　10　min　respectively.　However,　there　is　no　selectively　responds　to　other　anions.　Using　NMR　titration　and　theoretical　(B3LYP/6-31G　(d,　p))　methods　further　confirmed　the　hydrogen　bond　acceptor　molecules　and　anions.　©　2015　Chinese　Chemical　Society　&　SIOC,　CAS.