Herein,　a　variety　of　2,6-diaminopyridine　(DAP)　derived　nitrogen-doped　hierarchically　porous　carbon　(DAP-NHPC-T)　prepared　from　carbonization-induced　structure　transformation　of　DAP-Zn-SiO2-P123　nanocomposites　are　reported,　which　are　facilely　prepared　from　solvent-free　co-assembly　of　block　copolymer　templates　P123　with　pyridine-rich　monomer　of　DAP,　Zn(NO3)(2)　and　tetramethoxysilane.　In　the　pyrolysis　process,　P123　and　SiO2　templates　promote　the　formation　of　mesoporous　and　supermicroporous　structures　in　the　DAP-NHPC-T,　while　high-temperature　volatilization　of　Zn　contributed　to　generation　of　micropores.　The　DAP-NHPC-T　possess　large　BET　surface　areas　(approximate　to　956-1126　m(2)　g(-1)),　hierarchical　porosity　with　micro-supermicro-mesoporous　feature　and　high　nitrogen　contents　(approximate　to　10.44-5.99　at%)　with　tunable　density　of　pyridine-based　nitrogen　sites　(approximate　to　5.99-3.32　at%),　exhibiting　good　accessibility　and　reinforced　interaction　with　SO2.　Consequently,　the　DAP-NHPC-T　show　high　SO2　capacity　(14.7　mmol　g(-1),　25　degrees　C　and　1.0　bar)　and　SO2/CO2/N-2　IAST　selectivities,　extraordinary　dynamic　breakthrough　separation　efficiency　and　cycling　stability,　far　beyond　any　other　reported　nitrogen-doped　metal-free　carbon.　As　verified　by　in　situ　spectroscopy　and　theoretical　calculations,　the　pyridine-based　nitrogen　sites　of　the　DAP-NHPC-T　boost　SO2　adsorption　via　the　unique　charge　transfer,　the　adsorption　mechanism　and　reaction　model　have　been　finally　clarified.