Oxo-graphene nanoribbons (oxo-GNRs), created by unzipping single-wall carbon nanotubes (CNTs), are orthogonally functionalized at their rims and π-surfaces using hydrazine derivatives and diazonium salts. This study highlights successful sequential functionalization of up to 40 % edge atoms and 4 % basal plane atoms. Such modifications enhance oxo-GNRs’ potential in nanoelectronics and offer broader application possibilities for oxo-functionalized materials.