BiFeO3 nanofibers doped with divalent barium have been fabricated using electrospinning technique. Phase transition from space group R3c to C222 can be observed by the Ba doping. Our results indicate that these BiFeO3 nanofibers show obvious room temperature ferromagnetic behaviors, which can be enhanced remarkably with the increment of Ba doping. Microstructure and composition analysis indicates that barium effectively affected the magnetism after doping content was more than 5% and optical properties.