A Ce-doped photocatalytic composite with easy solid–liquid separation capability was prepared and a heterojunction was constructed between BiVO₄ and Fe₃O₄ via a co-precipitation method. A variety of characterization techniques were employed, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible spectroscopy (UV-vis), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), as well as other related methods. Its photocatalytic performance for the degradation of Rhodamine B (RhB) was also studied. The results indicate that the photocatalytic efficiency of BiVO₄/Fe₃O₄ is 1.4 times that of the pure BiVO₄ matrix. In particular, the photocatalytic efficiency of Ce_1.5%-BiVO₄/Fe₃O₄ was 2.2 times higher than that of the pure BiVO₄ matrix, and a 100% degradation rate of RhB was achieved within 30 min. The introduction of Fe₃O₄ not only forms a heterojunction with BiVO₄, increasing the active sites and surface oxygen vacancies of the material and effectively suppressing the recombination of photogenerated electron (e^-)-hole (h⁺) pairs, but it also enables the rapid separation of the material from the wastewater solution by the magnetic properties of Fe₃O₄. Additionally, the partial substitution of Ce for Bi in the BiVO₄ lattice reduces the bandgap energy, which enhances the utilization efficiency of visible light and improves the photocatalytic performance of the composite material. The mechanism of RhB degradation by Ce_1.5%-BiVO₄/Fe₃O₄ composite materials is also analyzed in this study. Quenching experiments and EPR tests revealed that h⁺ and ${·\mathrm{O}}_2^{-}$ were the primary reactive species in the degradation process.