In this paper, a two-step synthesis route combining an electrospinning technique and a solvothermal method has been accepted as a straightforward protocol for the exploitation of BiOCl–carbon nanofiber (CNF) hierarchical heterostructures. Photocatalytic tests showed that the BiOCl–CNF heterostructures possess a much higher degradation rate for 4-nitrophenol (4-NP) than pure BiOCl. The enhanced photocatalytic activity could be attributed to the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the BiOCl–CNF heterojunction interface. The OH˙ radicals played a critical role in the photocatalytic degradation of 4-NP over the BiOCl–CNF heterostructures. Moreover, the heterostructures could be recovered easily by sedimentation without a decrease in photocatalytic activity.