As evaluated with 15 crown ethers which contain varying numbers of benzo substituents, the magnitude of the extraction selectivities, (and in one case, the selectivity order) of aromatic group-containing ionophores for alkali metal picrates may vary significantly from those for alkali metal salts with inorganic anions as a result of pi-pi interactions between picrate ion and an aromatic unit of the ionophore. The importance of the "picrate effect" increases as the number of benzo groups in the crown ether is enhanced and varies with their location in the macrocycle. To verify the involvement of picrate-crown ether pi-stacking in complexation, crown ether-alkali metal picrate complexes were examined in solution by H-1 NMR spectroscopy and solid-state structures for nine complexes were determined by X-ray diffraction. Dependence of the chemical shift for the picrate proton singlet in the NMR spectrum on the metal cation and/or macrocycle identity in the metal picrate-crown ether complex was found to be a convenient tool for studying anion-ligand pi-pi interactions in solution.