The sulfonation of benzene-SO2X (X = CH3, OCH3, OH, and Cl) and of 1- and 2-naphthalene-SO2X (X = CH3, OCH3, and Cl) with sulfur trioxide in nitromethane as solvent has been studied. In the benzene series, substitution only occurs at the 3-position irrespective of X; the reaction rates, which are all within the same order of magnitude, are low. Upon sulfonation of the 1-SO2X-substituted naphthalenes, the main sulfonation product (58–80%) is the 5-sulfonic acid (5-S); in addition, 6-S and small amounts of 3-S and 7-S are formed. Also, the formation of the intermolecular sulfonic anhydride of 1-(methylsulfonyl)naphthalene-5-S is observed. The 2-SO2X-substituted naphthalenes all yield the 5-S and 8-S in a ratio of [Formula: see text] For both the benzene and naphthalene series, insertion of SO3 between the SO2 and X moieties of the chlorosulfonyl and methoxysulfonyl substituents proper takes place. In the benzene series these reactions are fast as compared with the actual ring sulfonation, whereas in the naphthalene series they are, in general, relatively slow. In the naphthalene series the mesomeric directing effect of the SO2X groups is less important than in the benzene series; the "naphthalene α-effect" also plays an important role.