A process for recovering and purifying substituted benzenesulfonates, by neutralizing a mixture including at least one substituted benzenesulfonate, or at least one corresponding substituted benzenesulfonic acid, and sulfur trioxide, sulfuric acid and/or hydrogen chloride in free or bound form, in an aqueous phase using an alkali metal hydroxide, and purifying it in this aqueous phase, and by subsequently separating the substituted benzenesulfonate(s) from this aqueous phase. The mixture is comminuted into particles having a Sauter mean diameter in the range from 1 nullm to 2 cm, either before or during introduction into this aqueous phase.