Two ligands, mono-β-diketone (p-methoxylbenzoyl)trifluoroacetone (MBTF) and bis-β-diketone 1,2-bis(4,4′-bis(4,4,4-trifluoro-1,3-dioxobutyl))phenoxyl ethane (BTPE) with similar chemical structures, have been designed and prepared for the purpose of building the relationship between the structures and luminescence properties of Eu(III) complexes. Structures of the Eu(III) complexes [Eu(MBTF)₃(DMSO)(H₂O)] and [Eu₂(BTPE)₃(DMSO)₄] have been defined by single crystal X-ray crystallography. The mono-β-diketone complex [Eu(MBTF)₃(DMSO)(H₂O)] is a mononuclear structure, the central Eu(III) ion is coordinated by eight oxygen atoms from three ligands and two solvents, in a distorted trigonal-dodecahedral (8-TDH) geometry. Whereas, the bis-β-diketone complex [Eu₂(BTPE)₃(DMSO)₄] adopts a triple-stranded dinuclear structure in which the two Eu(III) ions are helically wrapped by three bis-bidentate ligands, and each Eu(III) ion is eight-coordinated by six oxygen atoms from the ligands and two oxygen atoms from the coordinated DMSO molecules, in a distorted square-antiprismatic (8-SAP) geometry. The photophysical properties related to the electronic transition are characterized by the absorbance spectra, the emission spectra, the emission quantum yields, the emission lifetimes, and the radiative (k_r) and nonradiative rate constants (k_nr). The mono-β-diketone complex [Eu(MBTF)₃(DMSO)(H₂O)] offers a relatively high emission quantum yield (38%, in solid) compared to that observed in the bis-β-diketone complex [Eu₂(BTPE)₃(DMSO)₄] (25%, in solid). This enhancement of emission quantum yield in the mono-β-diketone complex can be attributed to its lower site symmetry around the Eu(III) ion, lower non-radiative rate constant and higher energy transfer efficiency from the ligand to the metal ion.