This paper reports the synthesis, structure, photophysical, and optoelectronic properties of five eight-coordinate Europium(III) ternary complexes, namely, [Eu(hth)3(L)2], bearing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (hth) as a sensitizer and L = H2O (1), dpso (diphenyl sulphoxide,2), dpsoCH3(4,4′-dimethyl diphenyl sulfoxide,3), dpsoCl (bis(4-chlorophenyl)sulphoxide,4), and tppo (triphenylphosphine oxide,5) as co-ligands. The NMR and the crystal structure analysis confirmed the eight-coordinate structures of the complexes in solution and in a solid state. Upon UV-excitation on the absorption band of the β-diketonate ligand hth, all complexes showed the characteristic bright red luminescence of the Europium ion. The tppo derivative (5) displayed the highest quantum yield (up to 66%). As a result, an organic light-emitting device, OLED, was fabricated with a multi-layered structure—ITO/MoO3/mCP/SF3PO:[complex5] (10%)/TPBi:[complex5] (10%)/TmPyPB/LiF/Al—using complex5as the emitting component.