TiO2 nanofibers were successfully prepared by electrospinning method using tetrabutyl titanate, glacial acetic acid, PVP and methanol as the precursors. Ag2O/TiO2 composite nanofibers were then prepared by decorating the surface of TiO2 nanofibers with Ag2O nanoparticles (NPs) through a wet-chemical precipitation reaction under a certain amount of AgNO3 and NaOH. The photocatalytic properties of the as-prepared samples were tested by photocatalytic decomposition of RhB aqueous solution under visible light irradiation. Comparing with bare TiO2 nanofibers and pure Ag2O, the Ag2O/TiO2 composite with optimal mass ratio of Ag2O to TiO2 (40 wt %) exhibited the highest photocatalytic activity in decomposition of RhB. The enhanced photocatalytic activity of the composite was attributed to the fast separation of the photo-generated electron-hole pairs in the Ag2O/TiO2 interface in which a p-n heterojunction is formed and the high visible light absorption efficiency of Ag2O/TiO2 nanofibers.