A 5¹² cage of (H₂O)₂₀ consisting of 30 hydrogen bonds encapsulates Astatide with little geometrical distortion. The cage is marginally destabilized but the non-covalent interactions are actually strengthened. Host⋯cage interactions in the [At@(H₂O)₂₀]⁻ cluster are anti-electrostatic, placing both negatively charged atoms in direct contact as in At^δ−⋯^δ−O–H^δ+. An orbital interaction analysis reveals that explicit host⋯cage contacts are “inverted” hydrogen bonds. That is, the same type of donor→acceptor charge transfer as in hydrogen bonding, with no proton bridging the two negative charges.