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Abstract In this work, Ag3PO4 microparticles were decorated onto the surface of BiFeO3 microcuboids through a precipitation method to obtain p-Ag3PO4/n-BiFeO3 heterojunction composites. The composites were employed for the degradation of acid orange 7 (AO7) under visible-light irradiation. It is found that the composites exhibit much higher photocatalytic efficiency than bare BiFeO3. Meanwhile, the intrinsical visible-light-driven photocatalytic activity of Ag3PO4/BiFeO3 composites was further confirmed by the degradation of phenol. In addition, the photo-Fenton-like catalysis property of the composite was also evaluated. The photocurrent analysis indicates that the combination of BiFeO3 with Ag3PO4 leads to the inhibition of recombination of photoinduced electrons and holes. The obvious enhancement in the photocatalytic activity of the composite is mainly ascribed to the efficient photogenerated charge separation and interfacial charge migration caused by the formation of Ag3PO4/BiFeO3 p-n heterojunctions.