The main aim of the present work is to precisely understand the sole effect of nitrogen doping on the electrochemical performance of porous carbon materials. To achieve this objective, the whole surface of mesoporous silica (SBA-15) was coated with a thin layer of carbon (about 0.4 nm) with and without N-doping by using acetonitrile and acetylene chemical vapor deposition, respectively. The resulting N-doped and nondoped carbon-coated silica samples have mesopore structures identical to those in the original SBA-15, and they are practically the same in terms of not only the pore size and pore structure but also the particle size distribution and particle morphology, with the exception of N-doping, which makes them unique model materials to extract the sole effect of nitrogen on the performances of electrochemical capacitors and electrocatalytic oxygen reduction. Moreover, the outstanding features of the carbon-coated silica samples allow even a quantitative understanding of the pseudocapacitance induced by nitrogen functionalities on the carbon surface in an acidic aqueous electrolyte.