Numerous strategies have been developed to improve the intensity of a luminol electrochemiluminescence (ECL) system due to the low quantum yield of luminol. Notably, considerable research was carried out to improve luminol ECL intensity relying on increasing the concentration of reactive oxygen species (ROS). Herein, a Co-Nx-C electrocatalyst treated with nitric acid or hydrochloric acid (named as Co-POC-O or Co-POC-R, respectively) was in situ prepared on the surface of carbon nanotubes. Surprisingly, compared with Co-POC-R, the Co-POC-O electrocatalyst not only displays excellent oxygen reduction reaction (ORR) performance but also enriches luminol via non-covalent bonds rather than covalent bonds and physical mixing. This method improves the amount of luminol involved in the electrochemical reaction as well as shortens the distance for electron transfer between oxidized luminol and ROS, which significantly enhances the ECL intensity (10-fold higher than that of the bare electrode and 2-fold higher than that of Co-POC-R). The platform realizes highly sensitive dopamine (DA) with a detection limit of 1.0 pM and a linear range from 10 pM to 1.0 nM. In this work, Co-POC-O is both the co-reaction accelerator and carrier material of luminophore species, which provides a new idea to realize ECL signal amplification.