Selective　capture　and　efficient　separation　of　SO2　from　industrial　emissions　are　critical　for　environmental　safety　and　public　health.　Nevertheless,　developing　cost-effective　adsorbents　with　high　capacity　and　improved　selectivity　remains　a　challenge.　Herein,　we　report　a　solvent-free　solidothermal　strategy　for　fabricating　edge-N　rich　porous　carbons　(NPC-x　series,　x　=　mass　ratio　of　ZnCl2　to　4,5-dicyanoimidazole)　via　ZnCl2-assisted　pyrolysis　of　Zn-coordinated　4,5-dicyanoimidazole　based　polymers.　The　series　of　materials　exhibit　highly　microporous　networks　with　high　BET　surface　areas　(up　to　1453.7　m2　g−1)　and　exceptionally　high　concentrations　of　edge-N　sites　(∼14.3　wt%).　Consequently,　the　optimal　NPC-x　sample　(NPC-5)　achieves　superior　SO2　adsorption　capacity　(14.8　mmol　g−1　at　25　°C　and　1　bar),　rapid　adsorption　kinetics,　and　exceptional　cycling　stability　over　20　adsorption-desorption　cycles.　Moreover,　NPC-5　demonstrates　outstanding　selectivity　for　SO2　over　N2,　with　an　impressive　IAST　selectivity　of　371　and　a　saturated　breakthrough　adsorption　capacity　of　1.77　mmol　g−1　under　simulated　flue　gas　conditions　(2　vol%　SO2/15　vol%　CO2/83　vol%　N2).　As　verified　by　theoretical　calculations,　the　enhanced　adsorption　performance　is　primarily　attributed　to　the　combined　effects　of　abundant　edge-pyridinic　and　pyrrolic　N　functionalities,　establishing　a　scalable　and　efficient　method　for　advanced　acid　gas　capture　and　separation　technologies.　©　2025　Elsevier　B.V.