In this paper, electrospinning method was used to prepare a one-dimensional nanostructured copper bismuthate-bismuth tungstate photocatalyst. The bismuth tungstate nanosheet structure was prepared by solvothermal method, and the copper bismuthate-bismuth tungstate precursor nanofibers were prepared by electrospinning using the doping method. The one-dimensional copper bismuthate-bismuth tungstate nanofiber structure was prepared by the high-temperature decomposition. The results show that the diameter of the bismuth tungstate and copper bismuthate nanofibers is about 280 nm, with continuous and regular fiber morphology. The fibers are composed of semiconductor nano-heterojunction and show good photocatalytic degradation efficiency for tetracycline hydrochloride. After 120 min of illumination, the degradation efficiency is greater than 90%, and it can be recycled and reused. The photocatalytic mechanism analysis showed that the energy band structure of the copper bismuthate-bismuth tungstate nano-semiconductor fiber was a Z-type heterojunction, and the free radical capture experiment showed that h+ and •O2− were main groups involved in oxidation reaction. The structure of high specific surface area of the nanofibers will improve the separation of photo-generated electrons and holes, and the experiment results show it has good performance of photocatalytic.