The aim of this work was to prepare BiFeO3 by modified solid-state sintering and mechanical activation processes and to investigate the structure and hyperfine interactions of the material. X-ray diffraction and Mössbauer spectroscopy were applied as complementary methods. In the case of sintering, BiFeO3 phase was obtained from the mixture of precursors with 3 and 5 % excess of Bi2O3 during heating at 1023 K. Small amounts of impurities such as Bi2Fe4O9 and sillenite were recognized. In the case of mechanical activation, the milling of stoichiometric amounts of Bi2O3 and Fe2O3 followed by isothermal annealing at 973 K resulted in formation of the mixture of BiFeO3, Bi2Fe4O9, sillenite and hematite. After separate milling of individual Bi2O3 and Fe2O3 powders, mixing, further milling and thermal processing, the amount of desired BiFeO3 pure phase was significantly increased (from 70 to 90 %, as roughly estimated). From Mössbauer spectra, the hyperfine interaction parameters of the desired BiFeO3 compound, paramagnetic impurities of Bi2Fe4O9 and sillenite were determined. The main conclusion is that the lowest amount of impurities was obtained for BiFeO3 with 3 % excess of Bi2O3, which was sintered at 1023 K. However, in the case of mechanical activation, the pure phase formed at a temperature by 50 K lower as compared to solid-state sintering temperature. X-ray diffraction and Mössbauer spectroscopy revealed that for both sintered and mechanically activated BiFeO3 compounds, thermal treatment at elevated temperature led to a partial eliminating of the paramagnetic impurities.