Polycyclic aromatic hydrocarbons (PAHs) are promising nanocarbon materials with diverse optoelectronic properties, yet they also pose concerning environmental and health risks. Despite the ubiquity of PAHs in the environment (crude oil, emissions, and biomass), most supermolecules rely on heteroatoms for stability. We discovered and characterized a family of all-hydrocarbon, all-π-conjugated [n]cycloparaphenylene-PAH host–guest complexes. We built a theoretical framework to rapidly select these complexes and predict their stabilities, driven exclusively by CH–π interactions. More than a dozen complexes were confirmed experimentally and assembled directly from commercially available compounds. This motif offers a versatile way to combine the advantageous properties of organic semiconductors with the rich dynamic, stereochemical, stimulus-responsive, and stress-dissipative behavior of host–guest complexes, while creating new opportunities for bespoke PAH separation or remediation materials.