BiFeO3 nanofibers doped with Ba and Mn have been prepared by an electrospinning method. The influence of Ba doping on the phase composition, microstructure, photocatalytic properties was investigated detailedly. Our results indicate that with the increase of Ba doped contents, the formation of impurity phase can be suppressed in these BiFeO3 nanofibers. A crystal lattice transformation occurred when 15 % Ba was doped. The degradation of Congo Red proved the enhanced photocatalytic behaviors in visible light region can be observed in these BFO nanofibers.