[eng] Several π-complexes of cations and anions with aromatic rings have been optimized at the MP2/6-31++G** level of theory. Different aspects of the cation−π interaction have been compared to those of anion−π, including changes in the aromaticity of the ring upon complexation, charge-transfer effects using the Merz−Kollman and "atoms-in-molecules" (AIM) charges, and the contribution of correlation and dispersion energies by comparing the complexation energies computed at the HF, B3LYP, and MP2 levels of theory. In this paper, we study three aromatic systems that allow direct comparisons, free from other influences, of the cation−π versus anion−π interactions, which are the 1,3,5-trifluorobenzene (TFB), s-triazine (TAZ), and 2,5-dichloropyrazine (DCP). These compounds are able to π-interact favorably with either anions or cations because of their very small quadrupole moments.