A novel ligand, 1-(naphthalen-2-yl)-2-(phenylsulthio) ethanone was synthesized using a new method and its two europium (Eu) (III) complexes were synthesized. The compounds were characterized by elemental analysis, coordination titration analysis, molar conductivity, infrared, thermo gravimetric analyzer-differential scanning calorimetry (TGA-DSC), H-1 NMR and UV spectra. The composition was suggested as EuL5 center dot(ClO4)(3)center dot 2H(2)O and EuL4 center dot phen(ClO4)(3)center dot 2H(2)O (L= C10H7COCH2SOC6H5). The fluorescence spectra showed that the Eu(III) displayed strong characteristic metal-centered fluorescence in the solid state. The ternary rare earth complex showed stronger fluorescence intensity than the binary rare earth complex in such material. The strongest characteristic fluorescence emission intensity of the ternary system was 1.49 times as strong as that of the binary system. The phosphorescence spectra were also discussed. Copyright (C) 2014 John Wiley & Sons, Ltd.