The structural and electronic properties of the capped (5, 5) single-walled carbon nanotube (SWNT), including the structural stability, the work function, and the charge transfer performance, are investigated for the substitutional nitrogen atom doping under different concentrations by first-principles density functional theory. The geometrical structure keeps almost intact with single or two N atom doping, while CN bonds may break up with serious defects for N concentrations of 23.3at.% and above. The SWNT remains metallic and the work function drops after doping due to the upward shift of Fermi level, leading to the increase of the electrical conductivity. N doping enhances the oxygen reduction activity stronger than N adsorption because of higher charge transfers.