For TiO₂-based photoanodes, the interfacial coupling between TiO₂ and conductive materials (e.g., carbon) plays a vital role in determining the electron transfer efficiency and thus photoelectrical performance. In this paper, we describe a facile approach to effectively engineering the interfacial coupling between reduced graphene oxide (RGO) and TiO₂ in well-designed one-dimensional (1D) RGO-wrapped TiO₂ nanofibers, which act as ultrafast electron transfer bridges when implanted in photoanodes. The 3–5 nm RGO nanoshells were hybridized with TiO₂ nanofibers as an electron donor component via d–π electron orbital overlap between C and Ti atoms, by adopting a thermal reduction at 450 °C. Remarkable photoelectric improvement, in terms of high photocurrent density by 2.2-fold and ultralow charge transfer resistance (R_ct) by 0.2-fold, is ascribed to the interfacial charge transfer. Completely reduced RGO in RGO/TiO₂ nanofibers was not necessary at the expense of their hydrophilicity, as it led to unexpected isolation in the photoanodes. The thermal reduction temperature of RGO/TiO₂ nanofibers was found to be critical, and a maximal photocurrent density could be achieved by 2.7-fold at 530 °C. An excess of RGO/TiO₂ nanofibers of more than 5 wt% had a degrading effect on the photoelectrical activity, largely due to the light-block effect and isolation in the matrix. This strategy provides new insight for tuning the intrinsic chemical and/or physical properties of well-designed semiconductor nanostructures with promising photoactivities in highly efficient photovoltaic devices.