Constructing elaborate catalysts to prompt the charge carrier separation and transport is critical to developing efficient photocatalytic systems. Here, a hierarchical hollow structure based on 1D/2D BiOCl/Bi2WO6 hybrid materials was fabricated by a precursor chemical engineering method. This hybrid is made up of molten 1D BiOCl nanorods and 2D Bi2WO6 nanosheets. The synergetic effect of the presence of BiOCl and specific interfaces between BiOCl and Bi2WO6 provided efficient interfacial charge transfer of photogenerated carriers under visible light. Seamless BiOCl functions like a noble metal, with platinum-like behavior, accelerating the oxidizing ability of fabricated BiOCl/Bi2WO6 hybrids, which was favorable for the photocatalytic decomposition of organic compounds (3.2 times greater for Rhodamine B (RhB) and 4 times greater for Ciprofloxacin (CIP)) over the Bi2WO6 catalysts. The beneficial interfacial interaction between BiOCl and Bi2WO6 resulting from the unique construction prompted the charge transfer from the conduction band of Bi2WO6 to that of BiOCl. The findings presented in this study provide a cost-effective precursor-mediated strategy to realize the critical and efficient separation of photoinduced carriers in environmental remediation applications.