Flexible hexatopic ligands, 1,2,3,4,5,6-hexakis(1H-naphtho[2,3-d]imidazol-1-ylmethyl)benzene (L(2)) and 1,2,3,4,5,6-hexakis(4,5-diphenylimidazol-1-ylmethyl)benzene (L(3)), containing six neutral naphthanoimidazolyl and 4,5-diphenylimidazolyl N donors were synthesized and used to assemble M6L6L'-type [M = Re(CO)3, L = anionic angular rigid NN donors, and L' = flexible hexatopic N donors] spheroid metallacycles. These molecules with a diameter of ∼17 Å were obtained from Re2(CO)10, H-L (imidazole, benzimidazole, and naphthanoimidazole), and L' [1,2,3,4,5,6-hexakis(benzimidazol-1-ylmethyl)benzene (L(1)), L(2), and L(3)] in a one-step process. Ligands L(2) and L(3) were characterized by elemental analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and (1)H NMR spectroscopy. Metallacycles 1-5 were characterized by elemental analysis, ESI-TOF-MS, Fourier transform infrared spectroscopy, and single-crystal X-ray diffraction analysis. Molecules 1, 2, and 4 can be considered as metallocavitands and contain multiple solvent-accessible receptors, i.e., two metallocalix[3]arene units and six/four calix[4]arene-/cleft-shaped receptors, on the surface. Guests such as acetone molecules could be accommodated in the calix[4]arene/cleft-shaped receptor of the metallocavitands.