Reaction of the tripodal ligands tris(N-alkylbenzimidazol-2-ylmethyl)amine with europium perchlorate affords the luminescent complexes [Eu(Rntb)(2)](ClO4)(3). nCH(3)CN . 0.5H(2)O (R = methyl, (n)propyl; n = 1, 2) in which the central Eu3+ ion is well encapsulated in a cubic coordination environment. Right- or left-handed Screw arrangement of the three arms of the ligand causes the cation [Eu(Rntb)(2)](3+) to be chiral, and two enantiomers crystallize together in complex [Eu((n)Prntb)(2)](ClO4)(3). 2CH(3)CN . 0.5H(2)O to give a racemer, but only one enantiomer is found in complex [Eu(Mentb)(2)](ClO4)(3). CH3CN . 0.5H(2)O.