A neutral self-assembled container synthesized from a concave π-extended tetrathiafulvalene (exTTF) ligand and the cis-Pd(dctfb)2(cod) complex (dctfb = 3,5-dichloro-2,4,6-trifluorobenzene; cod = 1,5-cyclooctadiene) is described. This molecular host exhibits a good binding ability for fused polyaromatic substrates. The corresponding inclusion properties are compared with those of a previously described analogous octacationic cage, offering therefore the opportunity to address the effect of the cavity charge state over the binding of neutral molecules.