The luminescent properties of europium(III) trifluoroacetate [Eu(TFA)3bipy·3H2O]∙bipy (I), where TFA - trifluoroacetate anion and bipy - 2,2′bipyridyl were investigated. Despite the presence of two efficient antenna ligands in complex (bipy1 in europium coordination sphere and bipy2 in the outer-sphere) the complex displays weak luminescence. By employing density functional theory-based methods, the luminescence, electron structure, interligand interactions and the processes of energy transfer in I were investigated. The nature of the chemical bond in I was studied by the natural bond orbital analysis. The mechanism of luminescence weakening in the complex was ascertained: competitive energy transfer from coordinated bipy1 ligand on to outer-sphere bipy2 molecule results in appreciable weakening of the antenna effect.