Many organic compounds of environmental concern contain amine groups that are positively charged at environmental pH. Here we present evidence that (hetero)aromatic amine cations can act as π acceptors in forming π(+)–π electron donor–acceptor (EDA) interactions with the π electron-rich, polyaromatic surface of pyrogenic carbonaceous materials (PCMs) (i.e., biochar, black carbon, and graphene). The π(+)–π EDA interactions combine a cation−π force with a π–π EDA force resulting from charge polarization of the ring’s quadrupole. Adsorption on a biochar and reference adsorbent graphite was conducted of triazine herbicides, substituted anilines, heterocyclic aromatic amines, and other amines whose charge is insulated from the aromatic ring. When normalized for the hydrophobic effect, the adsorption increased with decreasing pH as the amines became ionized, even on graphite that had no significant fixed or variable charge. The cationic π acceptor (quinolinium ion) was competitively displaced more effectively by the π acceptor 2,4-dinitrobenzene than by the π donor naphthalene. The maximum electrostatic potential of organocations computed with density functional theory was found to be a strong predictor of the π(+)–π EDA interaction. The π(+)–π EDA interaction was disfavored by electropositive alkyl substituents and by charge delocalization into additional rings. Amines whose charge was insulated from the ring fell far out of the correlation (more positive free energy of adsorption). Identifying and characterizing this novel π(+)–π EDA interaction on PCMs will help in predicting the fate of organocations in both natural and engineered systems.