In this paper, we evaluate the potential use of theoretical calculations to obtain an energy scale of the lowest ligand-centred triplet excited state in luminescent terbium(III) complexes. In these complexes, non-radiative deactivation of the terbium emitting state via a back-energy transfer process (T₁ ← Tb(⁵D₄)) is a common quenching process. Consequently the prediction of the energy gap between these two excited states should be useful for programming highly luminescent Tb^III systems. We report on a strategy based upon experimental and theoretical investigations of the excited state properties of a series of four simple aromatic hydroxamate ligands coordinated to Tb^III and Gd^III ions. By using previously reported crystallographic data, the structural and energies properties of these systems were investigated in the ground and first excited triplet states at the density functional theory (DFT) level of calculations. Our theoretical results are consistent with a triplet excited state T₁ which is localised on one ligand only and whose the energy level is independent of the lanthanide ion nature (Tb^III, Gd^III). A good agreement between the calculated adiabatic transition energies and experimental data derived from emission spectra is obtained when a corrective term is considered. These satisfactory results are an indication that this type of modelling can lead to discriminate in terms of the position of the lowest ligand triplet energy level the best antenna among a family of chromophoric compounds. In addition this theoretical approach has provided indications that the difference between the adiabatic transition energies of all the investigated complexes can be mainly explained by metal–ligand electrostatic interactions. The influence of the number of antennae on the quantum yield and the luminescence lifetime is discussed.