Currently, the development of photocatalysts with high activity and degradation of the emerging pollutants are two research hotspots in environmental field. Herein, a Z-scheme BiFeO3/Bi2O4 heterostructure was constructed by anchoring BiFeO3 nanoparticles on the Bi2O4 with a rod-like structure. The fabricated BiFeO3/Bi2O4 was characterized in detail by UV–vis spectra, XRD, XPS, SEM, and TEM. The photocatalytic decomposition of tetracycline (TC) was performed to assess the photocatalytic performance of BiFeO3/Bi2O4 under visible irradiation. The charge transfer pathway between BiFeO3 and Bi2O4 was clarified based on the band structure and the principal reactive species. BiFeO3/Bi2O4 presents exceptional activity for the photocatalytic degradation of TC. The degradation rate of TC reaches 92 %. The degradation rate constant (0.0847 min−1) of TC by BiFeO3/Bi2O4 was 8.7 and 20.7 times higher than that by Bi2O4 and BiFeO3, respectively. Besides, no obvious loss of activity was observed after 5 cycles of reuse, demonstrating the good stability of BiFeO3/Bi2O4. The significantly boosted activity of BiFeO3/Bi2O4 is because of the superior light-responsive ability and the highly efficient charge transfer resulting from the formation of a Z-scheme heterostructure between BiFeO3 and Bi2O4. The current work offers a new insight into constructing highly efficient composite photocatalysts.