The ORR electrocatalytic activity of nitrogen-doped carbon (N-doped carbon) is highly related to the type of nitrogen bondings, which is originated to the charge transfer between carbon and nitrogen. Based on Lewis theory of acid-base reactions, N-doped carbon can be defined as a Lewis base catalyst. The lone pair of electrons on the nitrogen atom mainly contributed to its reactivity, or in other terms, Lewis basicity. Herein, we fabricated selective amino-N, pyrrolic-N, nitrile-N, and oxide-N in N-doped carbon systematically, as well as compared their electrocatalytic activities and Lewis basicities for the first time. Based on the molecular structure of four starting precursors, aniline (C6H5NH2), pyrrole (C4H5N), benzonitrile (C5H7N), and nitrobenzene (C6H5NO2) were successfully formed as selective amino-N, pyrrolic-N, nitrile-N and oxide-N, respectively, via a room temperature plasma synthesis process. From the electrochemical performance, N-doped carbon catalyst with highly selective amino-N demonstrated comparatively higher ORR activity in terms of ORR onset potential and current density. Also, we confirmed the correlation between the ORR activity and Lewis basicity of various N moieties. Based on the electronic structural properties, amino-N with the most superior ORR activity also exhibited the highest basic strength among the studied C-N bonding structure. This study provided the relationship among the structural properties, Lewis basicity, and electrocatalytic activity of selective N-doped carbon.