Developing　supported　polytertiary　amine　solid　adsorbents　has　great　significance　for　highly　reversible　capture　of　SO2　from　industrial　tail　gas.　We　report　here　a　novel　solvent-free　molten　co-assembly　of　block　copolymer　templates　with　a　phenolic　precursor　and　silica　species　to　rationally　design　ordered　mesoporous　carbon-silica　nanocomposites,　silica　and　carbon　(OMC).　The　prepared　OMC　possesses　high　BET　surface　area　(1450　m(2)　g(-1)),　large　pore　volume　(1.8　cm(3)　g(-1)),　and　ordered　and　uniform　mesopores　(8.7　nm).　In　view　of　this,　the　methylated-polyethyleneimine　(mPEI)　was　physically　encapsulated　into　OMC,　and　the　synthesized　OMC@mPEI-x　were　systematically　characterized　and　investigated　for　selective　capture　and　separation　of　SO2.　In　comparison　with　many　other　supported　adsorbents,　the　OMC@mPEI-x　exhibit　excellent　performance　for　SO2　reversible　adsorption,　particularly　at　low　pressures　(9.0　mmol　g(-1),　25　degrees　C　and　0.1　bar),　giving　record　high　SO2/CO2　IAST　selectivity　(1789).　Meanwhile,　OMC@mPEI-x　also　displayed　superior　performance　for　continuous　separation　of　SO2　from　an　SO2/N-2/CO2　mixture,　and　their　saturation　breakthrough　sulfur　capacity　(6.9　mmol　g(-1),　25　degrees　C)　and　breakthrough　time　(775　min　g(-1),　25　degrees　C)　were　far　better　than　those　of　many　reported　solid　adsorbents,　demonstrating　that　they　can　be　applied　as　efficient　and　stable　solid　adsorbents　for　selective　adsorption　and　separation　of　SO2　from　industrial　processes.