Silyl-substituted pyrrolidines have gained increased interest for the design of new catalyst scaffolds. The molecular structures of four enantiomerically-pure 2-silylpyrrolidinium salts are reported. The perchlorate salts of (S)-2-(triphenylsilyl)pyrrolidine [(S)-1·HClO4] and (S)-2-(methyldiphenylsilyl)pyrrolidine [(S)-2·HClO4], the trifluoroacetate (S)-2·TFA, and the methanol-including hydrochloride (S)-1·HCl·MeOH were elucidated by X-ray crystallography and discussed in terms of hydrogen-bond interactions.