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This study presents theoretical and experimental investigations into the electron and hole color centers in BaFBr crystals, characterizing their electronic and optical properties. Stoichiometric BaFBr crystals grown by the Steber method were used in the experiments. Radiation defects in BaFBr crystals were created by irradiation with 147 MeV ⁸⁴Kr ions with up to fluences of 10¹⁰–10¹⁴ ions/cm². The formation of electron color centers (F(F⁻), F₂(F⁻), F₂(Br⁻)) and hole aggregates was experimentally established by optical absorption spectroscopy. Performed measurements are compared with theoretical calculations. It allows us to determine the electron transition mechanisms and investigate the processes involved in photoluminescence emission in Eu-doped BaFBr materials to enhance the understanding of the fundamental electronic structure and properties of electron and hole color centers formed in BaFBr crystals.