Dibenzyldiaza-18-crown-6 was utilised as a host to accommodate Nd(III) and Eu(III) metal ions together with thiocyanate as counter ion. The crystalline complexes formed were studied for their absorption in the infrared region and their crystalline structure by X-ray diffraction. The coordination of the metal ions to the counter ion and also to the donor atoms of the crown ether was clearly seen from the shift of the absorption band of the pure compound by up to nearly 15cm - 1 . From these absorption it was found that each lanthanide ion was coordinated to six donor atoms (2 N and 4 O) from crown ether and three donor atoms, N from NCS - . This nine coordination number complex was found to have the stoichiometry of 1:1:3 (crown ether:lanthanide; NCS - ). This ratio was further confirmed by X-ray crystallographic method. The lanthanide thiocyanate salts existed as an isolated (separate) entity in the center of the macrocyclic cavity. The three N atoms surrounded the Ln cation in a nearly planar trigonal arrangement with Ln ion being slightly out of plane. The trigonal plane was perpendicular to and bisects the plane of the macrocycle.