CeO2/black phosphorus (BP) heterostructure nanocomposite was synthesized via a two-step assembly method. The structure and optical property of the prepared composites were characterized by X-ray diffraction, transmission electron microscopy, UV–Vis diffuse reflectance spectroscopy (UV–Vis), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Photocatalytic degradation of bisphenol A (BPA) in simulated waste water was performed by using CeO2/BP nanocomposite as catalyst. Results indicated that the degradation rate of BPA reached 82.3% within 180 min, which was remarkably improved compared with pure CeO2 and BP due to the formation of indirect Z-scheme heterostructure intermediated by oxygen vacancies originated from CeO2. The unique heterostructure facilitated the charge transfer and preserved the high redox potential leading to improve the photocatalytic degradation performance.