Herein, a series of N-doped carbon nanotube (CNx) samples were obtained by modifying the synthesis temperature. Consequently, the proportion of graphitic nitrogen (N_graph) in the samples was systematically increased as a function of temperature. This allowed evaluation of the role of the CNx graphitic nitrogen in the oxygen reduction reaction (ORR). A correlation between the N_graph content and the ORR onset potential was observed, which shifted to more positive potentials with an increase in kinetic current density (j_k); this showed that N_graph played a significant catalytic role in the ORR. The samples with high N_graph content favored the two-electron pathway for the ORR not only in basic media (pH = 13) but also in neutral media (pH = 7), representing an attractive alternative for wastewater remediation through the on-site generation of H₂O₂. The energetic calculations showed that the formation of H₂O₂ must be favorable in the presence of graphitic nitrogen sites. Finally, the performance of the buckypaper arrangement was evaluated, and the CNx buckypaper showed a higher cathodic current peak as compared to CNx traditional ink dispersions. Overall, this study not only sheds light on the role of N_graph in the ORR, but also demonstrates that CNx buckypaper is an efficient 3D electrode for electrocatalytic applications.