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 (L3), 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 similar to 17 angstrom were obtained from Re-2(CO)(10), HL (imidazole, benzimidazole, and naphthanoimidazole), and L' [1,2,3,4,5,6-hexakis(benzimidazol-1-ylmethyl)benzene (L-1), L2, and L3] in a one-step process. Ligands L2 and L3 were characterized by elemental analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and H-1 NMR spectroscopy. Metallacycles 15 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.