A ytterbium(III) complex (C84H82Yb2N4O24) [Yb2(DMPA)6(phen)2] (phen=1,10-phenanthroline; HDMPA=3,4-dimethoxyphenylacetic acid (C12H12O4)) (CCDC: 757541) was synthesized and characterized by elemental analysis, infrared (IR) spectroscopy and thermogravimetry-derivative thermogravimetry (TG-DTG). Its crystal structure was determined by single crystal X-ray diffraction. The complex, C84H82Yb2N4O24, crystallizes in the monoclinic system in space group P1 with cell parameters of a=1.22877(14) nm, b=1.23235(16) nm, c=1.45234(19) nm, α=91.726(7)°, β=103.321(7)°, γ=113.885(6)°, cell volume: V=1.9379(4) nm3, number of molecules inside the cell: Z=1, relative molecular weight: Mr=1877.62, number of electrons: F(000)=946, density calculated: Dc=1.609 g·cm-3, absorptive parameter: μ(Mo Kα)=2.481 mm-1. The emission spectra of complexes doped with Eu or Tb (2.5%, 5.0%, 10.0%, molar fraction) instead of Yb were also investigated. The results showed that no luminescence emission peak was observed from emission spectrum of free ligand, and the luminescence behavior of complexes results from metal-centered emission. It is indicated that ligand can transfer the energy to the central metal efficiently and can sensitize the central metal.