The alkylammonium halogenoferrate families are subjected to diverse studies according to their wide field application. However, these compounds show various transitions depending on the preparation process. In this paper, the [(C₂H₅)₄N]FeCl₄ compound was successfully synthesized using a slow evaporation solution growth method at room temperature. An optical absorption measurement confirms the semiconductor nature with a band gap around 2.95 eV. The X-ray powder diffraction (XRPD) data confirmed the formation of a single-phase with hexagonal-type structure. The differential scanning calorimetry (DSC) indicated that the [(C₂H₅)₄N]FeCl₄ compound undergoes eight reversible phase transitions between 193 and 443 K. At high temperature (T > 423 K) the plastic nature of the crystals was confirmed. Temperature-controlled X-ray diffraction reveals that the thermal expansion of the crystal structure is non homothetic in the (a,b) plane and along the c axis. The temperature dependence of the Raman spectra up to 443 K revealed specific reorientations and molecular displacements of the organic and inorganic components associated with the phase transitions. We aim to thermally stabilize the [(C₂H₅)₄N]FeCl₄ compound which has a band gap suitable for photocatalytic processes.