The Fe2O3CaOTiO2BaSO4 system is established through miniature sintering experiments to reveal the mechanism of BaSO4 and vanadium‐titanium magnetite (VTM) with the help of X‐ray diffraction, scanning electron microscope and energy dispersive spectroscopy, and thermogravimetry. The results show that in the absence of BaSO4, the phase of the sinter consists of CaFe2O4, TiO2, Fe2O3, CaTiO3, and CaFe2O5. When the content of BaSO4 is 1% and 2%, CaTiO3 decreases and the number of needle‐like CF increases. Some Ba2+ solidly dissolve into CF and CaTiO3 to form trace BaFe12O19 and BaTi2O5. When the content of BaSO4 increases to 4%, the CaSO4 phase appears, the formation of C2F is accelerated, and the content of CF and CaTiO3 continues to decline. The needle‐like calcium ferrate gradually transforms into columnar and lamellar. As the BaSO4 content continues to increase to 6% and 8%, although the trend of each phase is similar to that at 4%, it is almost entirely composed of columnar calcium ferrite, barium ferrite, and incomplete tetragonal and rhombic Fe2O3. The results of the study provide a theoretical basis for the utilization of VTM and barium‐containing iron ores in practical production.