A series of ternary dinuclear europium(iii) complexes [Eu2(2,7-BTFDBC)3-n(DBM)2n(Phen)2] (n = 0, 1, or 2) were synthesized by using 2,7-bis(4'4'4'-trifluoro-1,3-dioxobutyl)-(9-ethyl-9H-carbazole) (2,7-BTFDBC), dibenzoylmethane (DBM), 1,10-phenanthroline (Phen) and europium(iii) ions. All these complexes display a broad excitation band in the blue region and high intensity emission with high colour purity. The intensity of emission significantly increases with the increase of DBM in [Eu2(2,7-BTFDBC)3-n(DBM)2n(Phen)2] (n = 0, 1, or 2). The theoretical predictions of the molecular geometry and electronic absorption spectrum of [Eu2(2,7-BTFDBC)(DBM)4(Phen)2] confirm that the pendant phenyl domains engage in multiple T-shaped and parallel-displaced π-stacking interactions with the coordination sphere of two europium(iii) centers. Using [Eu2(2,7-BTFDBC)(DBM)4(Phen)2] as a red phosphor, a single red LED has been obtained with a ∼460 nm-emitting GaN chip.