One-dimensional ZnO-carbon nanofibers (CNFs) heteroarchitectures with high photocatalytic activity have been successfully obtained by a simple combination of electrospinning technique and hydrothermal process. The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and IR spectrum. The results revealed that the secondary ZnO nanostructures were successfully grown on the primary CNFs substrates without aggregation. And, the coverage density of ZnO nanoparticles coating on the surface of the CNFs could be controlled by simply adjusting the mass ratio of zinc acetate to CNFs in the precursor during the hydrothermal process for the fabrication of ZnO-CNFs heterostructures. The obtained ZnO-CNFs heteroarchitectures showed high photocatalytic property to degrade rhodamine B (RB) because of the formation of heteroarchitectures, which might improve the separation of photogenerated electrons and holes. Moreover, the ZnO-CNFs heteroarchitectures could be easily recycled without the decrease in photocatalytic activity due to their one-dimensional nanostructural property.