The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host-guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B12X122- (χ = α, β, γ; X = H, F-I). Photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB1) or ionizing the host neutrals (RCB2), respectively, with the latter being substantially smaller than the former. Theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.