Novel carbon nanofibers with BiOBr and AgBr decoration have been prepared by a combination of electrospinning, carbonization and solvothermal treatments. BiOBr/AgBr hybrids interweaved together and covered the carbon nanofibers to form a three-dimensional (3D) open porous structure. The resultant composite carbon nanofibers exhibited a high efficiency for the photocatalytic degradation of RhB in aqueous solution and were convenient to separate from water.