In this work, BiFeO 3 powders were synthesized by a sol–gel method. The influence of annealing temperature on the structure and magnetic properties of the samples has been discussed. X-ray diffraction studies showed that the purest phase was formed in the temperature range of 400 °C to 550 °C and the samples annealed at a temperature below 550 °C were of nanocrystalline character. Mössbauer spectroscopy and magnetization measurements were used as complementary methods to investigate the magnetic state of the samples. In particular, the appearance of weak ferromagnetic properties, significant growth of magnetization, and spin-glass-like behavior were observed along with the drop of average grain size. Mössbauer spectra were fitted by the model assuming cycloidal modulation of spins arrangement and properties of the spin cycloid were determined and analyzed. Most importantly, it was proved that the spin cycloid does not disappear even in the case of the samples with a particle size well below the cycloid modulation period λ  = 62 nm. Furthermore, the cycloid becomes more anharmonic as the grain size decreases. The possible origination of weak ferromagnetism of the nanocrystalline samples has also been discussed.