AbstractHoley graphenic nanomaterials with porosity within the basal plane attract significant interest. It is observed that the perforation of graphene can enhance the specific surface area of the nanosheet, ensuring effective wetting and penetration of electrolytes to the electrode surface, facilitating rapid charge transfer, and boosting the electrocatalytic efficacy of the transducers. This study reports the first example of nitrogen‐doped holey reduced graphene oxide with a mesoporous morphology of the graphene basal plane (N‐MHG). It is shown that N‐MHG can be synthesized through a one‐step hydrothermal treatment of GO using NH₃ and H₂O₂. A straightforward procedure for the purification of N‐MHG has also been developed. AFM, TEM, and Raman analyses have revealed that N‐MHG possesses a highly mesoporous network structure with a pore size ranging from 10 to 50 nm. X‐ray photoelectron spectroscopy data have indicated a partial reduction of the graphene oxide sheets during the etching process but also show a 3–5 times higher content of C═O and O–C═O fragments compared to rGO. This could account for the remarkable stability of the N‐MHG aqueous suspension. An electrochemical sensor for dopamine analysis is assembled on a glassy carbon electrode with N‐MHG/Nafion membrane and characterized by cyclic voltammetry and electrochemical impedance spectroscopy.