Here we propose, for the first time, a new and green ethanol-thermal reaction method to synthesize highquality and pure thiophene–sulfur doped reduced graphene oxide (rGO), which establishes an excellent platform for studying sulfur (S) doping effects on the physical/chemical properties of this material. We have quantitatively demonstrated that the conductivity enhancement of thiophene–S doped rGO is not only caused by the more effective reduction induced by S doping, but also by the doped S atoms, themselves. Furthermore, we demonstrate that the S doping is more effective in enhancing conductivity of rGO than nitrogen (N) doping due to its stronger electron donor ability. Finally, the dye-sensitized solar cell (DSCC) employing the S-doped rGO/TiO₂ photoanode exhibits much better performance than undoped rGO/TiO₂, N-doped rGO/TiO₂ and TiO₂ photoanodes. It therefore seems promising for thiophene–S doped rGO to be widely used in electronic and optoelectronic devices.