The functionalization of graphene by nitrogen doping is an excellent method to modify the photocatalytic performance of graphene-based photocatalysts. However, the effect of N-bonding configurations (such as pyrrolic N, pyridinic N and graphitic N) on the photocatalytic performance of nitrogen-doped graphene/TiO₂ composite (N-rGO/TiO₂) has seldom been investigated. In this study, the different nitrogen sources (NH₃, N₂H₄, and CO(NH₂)₂) have been used to prepare the N-rGO/TiO₂ with the aim of obtaining different N-bonding configurations in graphene. It was found that when the NH₃ and CO(NH₂)₂ were used as the N-doping precursors, the resultant N-rGO/TiO₂ photocatalysts mainly showed the pyrrolic N (>70%) and pyridinic N (>10%). As for the N₂H₄ precursor, the prepared N-rGO/TiO₂(N₂H₄) primarily exhibited the pyrrolic N (ca. 63%) and graphitic N (ca. 37%) in graphene. The photocatalytic results indicated that all the N-rGO/TiO₂ showed an obviously enhanced photocatalytic performance compared with the undoped rGO/TiO₂. Moreover, the N-rGO/TiO₂(N₂H₄) displayed the highest photocatalytic activity (k = 0.29 min⁻¹), which is remarkably larger than that of TiO₂ and rGO/TiO₂ by a factor of 3.63 and 2.64, respectively. On the basis of the above results, a synergistic effect of graphitic N and pyrrolic N in graphene is proposed to account for the enhanced photocatalytic performance of N-rGO/TiO₂(N₂H₄), namely, the graphitic-N doped graphene serves as an effective electron-transfer mediator for the photogenerated electrons while the pyrrolic-N doped graphene functions as the oxygen-reduction active site to rapidly promote the following interfacial catalytic reaction. It is quite believed that the synthetic effect of electron-transfer mediator and oxygen reduction activation site is a general and effective strategy for the design of high-performance photocatalytic materials.