Disclosed is a complex of tiotropium bromide and polyvinylpyrrolidone (PVP), and a process for preparing said complex comprising preparing a solution of tiotropium bromide, PVP and a solvent, concentrating the solution under vacuum to obtain a residue, and drying the residue to obtain the tiotropium bromide-PVP complex. Further disclosed are processes for preparing said complex comprising preparing a solution of tiotropium bromide, PVP and a solvent, and either flash-evaporating the solvent or freeze-drying the solution and lyophilizing the freeze-dried solution. Also disclosed is a pharmaceutical composition comprising a tiotropium bromide-PVP complex that is adapted for inhalation.