Nucleophilic substitution of 4-(dimethylamino)pyridine on pentachloropyridine yielded pentakis(pyridine-2,3,4,5,6-pentayl)pyridinium, tris-(3,5-dichloropyridine-2,4,6-triyl)pyridinium, or (tetrachloropyridin-4-yl)pyridinium depending on the reaction conditions. Nucleophilic substitution with water, hydroxides, and alcoholates resulted in new betaines and highly substituted pyridines. [structure: see text]