The self-assembly between the amidothiourea ligands 1 and 2 and Tb(III) gave rise to the formation of 1:1 and 3:1 (ligand-Tb) supramolecular architectures that were shown to be luminescent in both MeOH and in water-DMSO solutions; preliminary investigations in the latter system also showed that their emission was modulated upon interacting with anions such as acetate and phosphate due to host-guest formation.