Bi0.90Sm0.1Fe0.97Cr0.03O3@PANI core-shell structures were made by a two-step method, first, bismuth ferrite nanoparticles by hydrothermal method and then, aniline core-shell by co-precipitation method. The bismuth ferrite (BFO) XRD pattern showed no impurities of Sm, Cr, or their compounds in the samples, indicating that Sm+3 and Cr+3 had been replaced in the BFO structure. The XRD pattern of the Bi0.90Sm0.1Fe0.97Cr0.03O3@PANI core-shell shows all peaks of Bi0.90Sm0.1Fe0.97Cr0.03O3 composition with lower intensity, as a result, the Bi0.90Sm0.1Fe0.97Cr0.03O3 composition is phase single. This lower intensity is attributed to the presence of amorphous polyaniline in the core-shell structure. Since there is in the FT-IR spectrum of the Bi0.90Sm0.1Fe0.97Cr0.03O3@PANI core-shell, characteristic peaks of both polyaniline and bismuth ferrite simultaneously so, the FT-IR spectrum of the Bi0.90Sm0.1Fe0.97Cr0.03O3@PANI core-shell is a perovskite structure. The synthesized samples exhibit weak magnetic properties and behave as a paramagnetic material. The absorption capability of core-shell compared to core nanoparticles has increased in the visible region, and this enhancement is attributed to the influence of the presence of polyaniline. All the peaks in the UV–visible absorption spectrum characterize the nano-sized bismuth ferrite and polyaniline in the UV–visible spectrum of the core-shell. The intensity of the photoluminescence spectrum in the doped sample is significantly higher compared to the core-shell sample. This indicates a much faster recombination rate in the doped nanoparticles compared to the core-shell nanocomposite. The doping of the core with Cr and Sm elements, as well as the coating of the core with a polymeric shell, has led to an increase in the degradation rate of the red dye. We also found that shell thickness plays a vital role in dye degradation efficiency and photocatalytic performance. The Bi0.90Sm0.1Fe0.97Cr0.03O3@PANI core-shell exhibits significant photocatalytic activity under visible light. The photocatalytic studies show that the best sample is Bi0.9Sm0.1Fe0.97Cr0.03O3@PANI core-shell with aniline concentration of 0.2 mL and a pH = 2 which was able to destroy 100 % of Congo red dye molecules.