Nitrogen (N)-doped nanostructured carbons have been actively examined as promising alternatives for precious-metal catalysts in various electrochemical energy generation systems. Herein, an effective approach for synthesizing N-doped single-walled carbon nanohorns (SWNHs) with highly electrocatalytic active sites via controlled oxidation followed by N2 plasma is presented. Nanosized holes were created on the conical tips and sidewalls of SWNHs under mild oxidation, and subsequently, the edges of the holes were easily decorated with N atoms. The N atoms were present preferentially in a pyridinic configuration along the edges of the nanosized holes without significant structural change of the SWNHs. The enriched edges decorated with the pyridinic-N atoms at the atomic scale increased the number of active sites for the oxygen reduction reaction, and the inherent spherical three-dimensional feature of the SWNHs provided good electrical conductivity and excellent mass transport. We demonstrated an effective method for promoting the electrocatalytic active sites within N-doped SWNHs by combining defect engineering with the preferential formation of N atoms having a specific configuration.