Despite that hydrogen is an attractive energy source, there are two situations regarding its use: The hydrogen storage and the catalyst use for optimizing its conversion into energy. N-doped carbons are considered serious candidates for hydrogen storage and catalysis. Hence, this paper reports a one-pot and controllable strategy to obtain porous N-doped carbons with a monolith-type morphology, high surface area, and hierarchical porosity. The presence of nitrogen increases electron donor and wettability of carbons, which is favorable for their use in hydrogen adsorption and electrodes. The method is based on using aniline as a carbon source and its polymerization in a Pluronic F127 micellar system before carbonization. It is shown that the pore size and pore volume of porous carbon can be effectively tuned by using tetraethyl orthosilicate (TEOS). The relation between aniline polymerization conditions, surface chemistry, and porous carbon properties was also studied. The polyaniline permitted a high conversion to carbon (43,5 – 98,1 %) and nitrogen content of 5 % wt in the N-doped carbon. Besides the well-developed porosity and interesting monolithic morphology, the electrochemical characterization showed that increasing the temperature of carbon synthesis improved the electroactive performance due to the higher graphitization. Besides, the hydrogen diffusion showed a high value compared with other carbon materials. In this way, better charge transfer and favorable diffusion pathways were achieved by combining doping and hierarchical porosity. So, we show that the pore size and the surface area affected the electrochemical properties and the hydrogen diffusion in this type of carbon.