By employing electrospun TiO2 nanofiber as substrate, rare earth Ce doped Bi2MoO6/TiO2 composite nanofibers were prepared via solvothermal method. The composition, morphology and optical properties were characterized by XRD, SEM, XPS, TEM, UV-Vis DRS and PL analysis. The photocatalytic properties were tested by degradation of rhodamine B under visible light. The results show that Ce3+ ion can be a substitute for Bi3+ in the crystal lattice of Bi2MoO6, resulting in an expansion, distortion of lattice cell and hence defects. Photocatalytic test shows that the activity of TiO2 nanofibers under visible light can be enhanced. For example, the degradation percentage of RhB can be as high as 95.1%, which is believed to benefit from the effective charge generation, transfer and separation at the interface of Ce-doped Bi2MoO6/TiO2 heterojunction. Moreover, the Ce-doped Bi2MoO6/TiO2 composite nanofibers are of good stability, whose activity is hardly decreased after cycling 5 times.