Fe-doped TiO2 nanofibers with a thoroughly mesoporous structure were prepared via a facile foaming-assisted electrospinning method. The foaming agents and FeAcAc were introduced in the raw materials to create the mesopores and incorporate the Fe dopants into the conventional solid TiO2 nanofibers, respectively, which could be accomplished simultaneously over a one-step calcination process. The photocatalytic experimental results demonstrate that the mesoporous Fe-doped TiO2 nanofibers exhibit significantly enhanced activity toward the RhB degradation and splitting water for hydrogen generation under visible-light illumination, as compared to those of Fe-doped solid and intrinsic thoroughly mesoporous counterparts. The photocatalytic mechanism is proposed that the one-dimensional mesoporous nanostructure can enhance the transportation of the reactant and products, and the Fe-doping induces the shift of the absorption edge into the visible-light range and restrains the recombination of photo-generated electrons and holes, which can synergistically improve their activity.