The present study gives a comprehensive insight into anion–π interactions in the solid state, focusing on purely organic and charge-neutral fluorophenyl groups bearing a positive charge located at a side chain. The detailed statistical analysis of a series of structural data sets shows the geometrical variability of anion–π bonding in the solid state. It reveals the directing substituents at the arene as key elements for the positional preferences of anions above π-systems. The structural variety of the interaction between anions and electron-deficient arenes is considered by use of the hapticity concept. Together with new evaluation criteria, two helpful tools to understand and describe anion–π interactions in the solid are used.