The structure and detailed electron density distribution (EDD) of the large octanuclear chromium-wheel host complex [Cr₈F₈(tBuCO₂)₁₆] (1) has been determined from synchrotron X-ray structure factors collected at 16(5) K. The complex has a central cavity with a minimum entry distance between carbon atoms of the pivalate methyl groups (pivalic acid = tBuCO₂H) of 4.027(4) Å on one side of the molecule and 7.273(4) Å on the other. The screened side of the molecule can be "opened" by rotation of methyl groups to create a strained host structure, which is compensated for by improved host - guest and host - solvent interaction. The EDD of the 272-atom complex (1144 e^-) was determined by multipole modeling based on the experimental structure factors. 3d orbital populations on the Cr atoms and topological analysis of the EDD show that the covalent part of the metal-ligand interactions consists mainly of σ donation from the ligands, but that overall the interactions are predominantly electrostatic. The electrostatic potential (EP) has been calculated from the experimental EDD. Knowledge of the geometry of the naked complex 1 as well as the EP in the central cavity of this molecule allows us to deduce which characteristic properties guest molecules must have to be accepted into the void. To probe these predictions, a series of complexes of 1 with different guest inclusions were synthesized (2 = 1 + N,N′-dimethylformamide (DMF), 3 = 1 + N,N′-dimethylacetamide (DMA), 4 = 1 + DMA + DMF, 5 = 1 + 2CH₃CN), and their structures were examined by using X-ray diffraction data measured at 120(1) K. Results of these studies indicate that in the crystalline state, the optimal guest molecule should be linear and possess a permanent dipole. Attempts to crystallize the host complex with cations incorporated into the cavity were fruitless, although electrospray ionization mass spectrometry showed that a [1 + potassium]⁺ entity pre-exists in solution and can be transferred intact into the gas phase.