Abstract The composition of some aromatic terbium carboxylates TbL 3 (HL = Hpobz: 2-phenoxybenzoic acid; HPA: phenylanthranylic acid; HSal: salicylic acid; Habz: anthranylic acid) and their mixed-ligand complexes TbL 3 (TPPO) n (TPPO: triphenylphosphine oxide; n = 1, 2) was studied by direct laser desorption/ionization mass spectrometry (LDI MS). The influence of the ligands composition on the oligomerization of complex molecules and stability of oligomeric ions during LDI MS experiment was established.