We developed a strategy for manipulating the binding strength of polycyclic aromatic hydrocarbons (PAHs) via covalent post-assembly modification (PAM) of tetranuclear ruthenium macrocycles containing s-tetrazine ligands. The macrocycles act as efficient receptors for various PAHs. Inverse electron demand Diels–Alder (IEDDA) reaction of the macrocycles was applied to reduce the binding ability significantly.