The complexation behavior of two novel, chiral pinene–bipyridine-type ligands ((–)-HL1 and (–)-HL2) containing a carboxylic arm towards lanthanide Ln(III) (Ln = La, Eu, Lu) ions was investigated through spectroscopic methods. The association constants of the mononuclear complexes determined from the UV-Vis titrations indicated that the ligand (–)-HL1 possessing a shorter carboxylic arm formed more stable complexes compared with (–)-HL2, whose carboxylic arm had one more methylene unit. This is due to the formation of more stable seven-member metal chelate rings in the first case as compared with the eight-member metal chelate rings in the second. IR and fluorescence spectroscopy provided additional information about the structure of these complexes.