A mild and efficient catalytic method for Friedel–Crafts sulfonylation of arenes to the corresponding sulfones using a catalytic amount of reusable solid acid and arene- or alkanesulfonyl chlorides, sulfonic anhydrides and sulfonic acids as sulfonylating agents is described. Solid acids enable formation of a sulfone by the reaction of a sulfonic acid and an arene for the first time. In pursuit of the development of the best catalytic system, various metal-exchanged K10 montmorillonites and synthetic zeolites such as zeolite beta, zeolite Y and ZSM-5 have been screened for Friedel–Crafts sulfone synthesis. Fe³⁺-montmorillonite in the family of clays and zeolite beta in the family of zeolites exhibit higher activity. The activity is correlated to the presence of the right mix of Brønsted and Lewis acidic sites. The regioselective sulfonylation of toluene and naphthalene are studied in which para and beta selectivities are observed respectively.