| Summary: | As a hazardous waste, water pickling liquors must be properly treated. An alternative consists of promoting the formation of ferrous salts from this residue due to their higher ferrous content. Since FeCl<sub>2</sub>·4H<sub>2</sub>O is widely used in several applications, obtaining pure crystals of this material appears to be an interesting prospect. However, this compound has scarcely been investigated. In the present work, FeCl<sub>2</sub>·4H<sub>2</sub>O crystals were obtained from water pickling liquors. Their structural and morphological characteristics were investigated by X-ray diffraction, scanning electron microscopy as well as Mössbauer spectroscopy. In addition, the photoluminescence study of the obtained samples was also assessed. It was observed that after some aging time, the obtained crystals changed in colour from green to more yellowish. As such, the aged sample was also evaluated, and their structural characteristics were compared with the original crystals. Despite this, the obtained crystals exhibit a FeCl<sub>2</sub>·4H<sub>2</sub>O structure, which is not modified with the aging of the sample.
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