A series of zirconium-carboxylate metallocavitands with the general formula [(CpZr)(3)(mu-kappa(2),O',O '' CR)(3)(mu(3)-O)(mu(2)-OH)(3)]Cl (Cp = cyclopentadienyl; R = C5H4N (5), C6H2N (6), C18H14N (7), and C18H12N (8)) were synthesized in moderate to high yields (40-83%) by reacting the corresponding carboxylic acids 1-4 with Cp2ZrCl2 in a self-assembly procedure at room temperature. The metallocavitands were characterized using H-1 and C-13 NMR spectroscopy and by single-crystal X-ray diffraction. Complexes 7 and 8 exhibit efficient photoluminescence properties in solution. The photoluminescence peak of 7 was observed at 464 nm and that of 8 at 422 nm with respective quantum yields in solution of 87 and 65%.