The one-step synthesis method of nitrogen doped microporous carbon monoliths derived from biomass with high-efficiency is developed using a novel ammonia (NH3)-assisted activation process, where NH3 serves as both activating agent and nitrogen source. Both pore forming and nitrogen doping simultaneously proceed during the process, obviously superior to conventional chemical activation. The as-prepared nitrogen-doped active carbons exhibit rich micropores with high surface area and high nitrogen content. Synergetic effects of its high surface area, microporous structure and high nitrogen content, especially rich nitrogen-containing groups for effective CO2 capture (i.e., phenyl amine and pyridine-nitrogen) lead to superior CO2/N2 selectivity up to 82, which is the highest among known nanoporous carbons. In addition, the resulting nitrogen-doped active carbons can be easily regenerated under mild conditions. Considering the outstanding CO2 capture performance, low production cost, simple synthesis procedure and easy scalability, the resulting nitrogen-doped microporous carbon monoliths are promising candidates for selective capture of CO2 in industrial applications.