The present contribution uses a valence bond (VB) perspective to consider the captodative substitution strategy, a method to enhance the diradical character of (potentially aromatic) compounds. We confirm the qualitative reasoning that has generally been used to rationalize the diradical-character-enhancing effect of captodative substitution: this type of substitution scheme disproportionally stabilizes specific Dewar/diradical(oid) VB structures, thus increasing their weight in the full ground-state wave function. Furthermore, we assess the effect of captodative substitution on the aromaticity of the considered compound. We observe a clear trade-off between diradical character and aromaticity for our model systems: as one of these properties increases, the other decreases. This finding is especially significant within the field of single-molecule electronics because it enables unification of the previously observed inverse proportionality between the aromaticity of a compound and the magnitude of conductance through that molecule, with the observed proportionality between diradical character and the magnitude of conductance associated with a compound. To some extent, both properties, i.e., aromaticity and diradical character, appear to be the flip-sides of the same coin.