The films generating photoluminescence have unique properties for various applications. In this work, the chemical or covalent bonding between unsaturated linear polyester (ULP) containing rare earth Europium (Eu) complex (Eu-ULP) and polypropylene (PP) was introduced through a melt-grafting polymerization, which led to an improved approach for the preparation of photoluminescent films. Eu-ULP was synthesized, and then grafted onto PP in melt phase to render the resin fluorescence-active. The grafted PP was systematically characterized using various analytic tools including TG, IR, DSC, WAXS and fluorescence. The results indicated that Eu-ULP was covalently grafted onto polypropylene backbones. The findings from DSC and WAXS measurements revealed that Eu-ULP acted as a nucleating agent, increasing the crystallization rate effectively and destroying the integrity of crystalline as well.