Multiferroic nanocrystalline Bi[Formula: see text]Sr[Formula: see text]FeO3 ([Formula: see text], 0.05, 0.1) samples were synthesized using the sol–gel method and characterized by powder X-ray diffraction, Mössbauer spectroscopy and SQUID system. The small-angle X-ray diffraction analysis showed that the sample underwent phase transition from rhombohedral to pseudo-cubic structure with the enhancement of Sr content. In addition, impurity peaks gradually diminished, indicating that content of impurities of samples reduced. Furthermore, it can be determined that there is only Fe[Formula: see text] in all the samples and impurity phase that existed in the samples was Bi[Formula: see text]FeO[Formula: see text] by fitting Mössbauer spectra. It is further confirmed that Bi[Formula: see text] Sr[Formula: see text]FeO3 samples were generated by oxygen vacancy equilibrium valence state when Sr[Formula: see text] ions replaced Bi[Formula: see text] ions. The change of quadrupole splitting indicated that a low concentration of Sr[Formula: see text] ions diffused homogeneously in the sample. Magnetization measurement showed that the magnetization of the sample increased gradually with the substitution of Bi[Formula: see text] by nonequivalent Sr[Formula: see text] ions, which can be ascribed to the decrease of grain size and the increase of oxygen vacancy and specific surface in the samples.