Based on molecular design, starburst europium(Ⅲ) β-diketonate complex tris(dibenzoylmethanato){1,3,5tris[2(2′pyridyl)benzimidazoly]methylbenzene}europium(Ⅲ) (Eu3(DBM)9(TMMB)) was synthesized. An organic photovoltaic (PV) device, in which 4,4′,4″tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) and Eu3(DBM)9(TMMB) are used as an electron donor and an acceptor, respectively, has been fabricated by a vacuum deposition method. Under the illumination of UV light (365 nm, 1.6 mW/cm2 ) , the open circuit voltage, short circuit current dencity, fill factor and power conversion efficiency of the PV device were measured to be 1.70 V, 38.9 μA/cm2, 0.25 and 1.05%, respectively. These results indicate that the starburst europium(Ⅲ) β-diketonate complex showed good PV performance.