Using 2′-Hydroxyacetophenone and as the raw material, 1-(2-Hydroxyphenyl)-3-Phenyl-1,3-Propanedione (HPPPD) was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HPPPD with europium were also synthesized. The compounds were characterized by IR, thermo-gravimetric analysis and ~1H-NMR. The effects of phenolic hydroxyl on the luminescence properties of complexes were studied. The results show that the complexes emit strong red fluorescence and the fluorescence intensity of the ternary complex is better than that of the duality. But the complexes of HPPPD with Sm(Ⅲ), Tb(Ⅲ), Dy(Ⅲ)emit weak fluorescence. The phenomenon was interpreted by electron-effect and energy-matching mechanism. Energy transfer mechanism of the luminescence in the complex was discussed. Using 2’-Hydroxyacetophenone and as the raw material, 1- (2-Hydroxyphenyl) -3-Phenyl-1,3-Propanedione (HPPPD) was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HPPPD with europium were also synthesized. The compounds were characterized by IR, thermo-gravimetric analysis and ~ 1H-NMR. The effects of phenolic hydroxyl on the luminescence properties of complexes were studied. The results show that the complexes emit strong red fluorescence and the fluorescence intensity of the ternary complex is better than that of the duality. But the complexes of HPPPD with Sm (Ⅲ), Tb (Ⅲ), Dy (Ⅲ) emit weak fluorescence. The phenomenon was interpreted by electron-effect and energy-matching mechanism. of the luminescence in the complex was discussed.