Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L-1) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L-2), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO4)(3) (series A), [LnL(1) (Antipy)Cl(H2O)(2)]Cl-2(H2O)(2) (series B), and [LnL(2)(NO3)(3)] (series C). The nitrate salt of the free ligand H2L1.(NO3)(2) and six complexes were structurally characterized: Pr(3+)A, Y-3+A, Eu3+B, Eu3+C, Gd3+C and Tb3+C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L-1 and L-2 exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl- dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO3- ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (LC)-L-3 level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L-1 and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.