The synthesis of chloro formamidinium chloride has been known for over one century. However, no solid-state structure of a chlorine-substituted formamidinium compound has been reported up to now. In this contribution, the syntheses, solid-state structures, and vibrational properties of four chloro formamidinium compounds are described. The full paper can be accessed via https://doi.org/10.1002/zaac.201800164