In this paper, hierarchical nanostructures of BiOBr/AgBr on electrospun carbon nanofibers (CNFs) were prepared by combination of electrospinning and carbonization. Compared with the smooth surface of CNFs, the rough surface with hierarchical nanostructures of BiOBr/AgBr can be obtained by adding the certain amount of BiOBr/AgBr precursors into the spinning solution. The as-prepared composite CNFs exhibited highly photocatalytic activities for degradation of rhodamine-B and reduction of p-nitrophenol under the visible-light irradiation and at room temperature. Furthermore, the as-prepared composite CNFs showed the favor separation, recovery, and cyclic utilization properties.