The polarization processes in Bi12SiO20 crystals doped with Fe (Bi12SiO20 : Fe) in the temperature interval 300–800 K are studied by the thermoactivation spectroscopy methods. The temperature dependences of the thermostimulated depolarization (TSD) currents and the dependences of the intensities of TSD current peaks on the polarization conditions are obtained. The mechanisms of space charge and quasidipole polarizations are revealed. The temperature dependences of the optical absorption of Bi12SiO20 : Fe crystals are also investigated.