A new salicylic-based open-chain crown ether ligand, 1,10-bis(2'-carboxylphenyl)-1,4,7,10-tetraoxadecane (BCPTD) was synthesized. Solutions of its complex with Tb3+ can emit the intrinsic fluorescence of Tb3+. The fluorescence intensity of the complex in KCl solution was enhanced by the addition of silver (I), leading to a new fluorescence enhancement phenomenon. The spectrofluorimetric determination of traces of silver (I) based on the above phenomenon was carried out. The excitation and emission wavelengths are 298 and 545nm, respectively. Under optimal conditions, the differenial value of fluorescence intensity in the absence and presence of Ag+ was proportional to the concentration of silver (I) in the range 0.5-20μgml−1. The method was applied to the determination of silver (I) in a standard ore sample. The analytical performance is investigated in detail by using common aromatic carboxylic acids or synthetic analogues of BCPTD as ligands to replace BCPTD. It was found that Tb-aromatic acid complexes did not result in fluorescence enhancement of Tb3+ in AgCl collosol. The phenomenon was only observed in Tb (III) with BCPTD or its open-chain crown ether analogues solutions. In addition, the enhancement of the fluorescence intensity of terbium (III) in these complexes depends on the extent of formation of the AgCl collosol.