Preparation of new tiotropilium salts (1) by subjecting a different tiotropilium salt (2) to anion exchange with an ion source in a solvent. Preparation of new tiotropilium salts of formula (1) by subjecting a different tiotropilium salt of formula (2) to anion exchange with an ion source (Kat-X) in a solvent. [Image] X : anion; Y : anion, different from X, i.e. halo, 1-10C alkyl-sulfonate or -sulfate, or 6-10C arylsulfonate; Kat : cation. An independent claim is also included for new compounds (1) and (2), except where Y/X = bromo, optionally as solvates or hydrates. ACTIVITY : Antiasthmatic. No details of tests for antiasthmatic activity are given. MECHANISM OF ACTION : Anticholinergic.