BACKGROUND Acetamidines are starting materials for synthesizing many chemical substances, such as imidazoles, pyrimidines and triazines, which are further used for biochemically active compounds as well as energetic materials. The aim of this study was to synthesise and characterise a range of acetamidinium salts in order to overcome the inconvenience connected with acetamidinium chloride, which is the only commercially available acetamidinium salt. RESULTS Acetamidinium salts were synthesised and characterised by elemental analysis, mass spectrometry, NMR and - in the case of energetic salts - DTA. The structures of previously unknown acetamidinium salts were established by X-ray diffraction analysis. Hygroscopicities in 90% humidity of eight acetamidinium salts were evaluated. CONCLUSIONS The different values of hygroscopicity are corroborated by the structures determined by X-ray analysis. The acetamidinium salts with 2D layered structures (acetamidinium nitrate, formate, oxalate and dinitromethanide) show a lack of hygroscopicity, and the compounds with 3D type of structure (acetamidinium chloride, acetate, sulphate and perchlorate) and possessing rather large cavities are quite hygroscopic.