Sn doped ZnO microspheres stringed on carbon fibers composites like sugar-coated haws on a stick were successfully prepared by a precursor method. Firstly, Sn doped Zn5(CO3)2(OH)6 microspheres were successfully formed on carbon fibers. Then, after calcination, Sn doped ZnO microspheres stringed on the carbon fibers composites were successfully obtained. X-ray diffraction (XRD), field emission scanning electronic microscope (FESEM), and transmission electron microscope (TEM) were used to characterize the products. The studies of photocatalytic degradation on Methylene blue (MB) indicate that the composites show enhanced visible-light-driven photocatalytic activities for degradation of organic pollutants. Furthermore, the free-standing Sn doped ZnO/carbon fibers composites can be easily thrown into and recovered from a wastewater solution with stable recycling performance. This work provides a facile method for the preparation of carbon fibers based composite materials, which may have potential applications in the environment field.