The　amine-based　materials　pose　high　potential　for　the　adsorption　of　sulfur　dioxide　(SO2).　This　work　is　aimed　at　modulating　the　morphologies　of　SBA-15　adsorbents　by　controlling　the　precursor　self-assembly　processes,　for　the　sake　of　optimizing　the　utilization　efficiency　of　amine　species　in　the　polytertiary　amine　(PTA)-functionalized　SBA-15.　It　results　that　worm-like　SBA-15　(WLS)　material　shows　a　better　particle　aspect　ratio　and　well-defined　pore　structure,　which　helps　to　optimize　the　adsorption　sites　invoked　by　the　preferable　dispersion　and　exposure　of　PTA,　thus　amplifying　the　chemisorption　of　SO2　on　the　adsorbent.　Consequently,　the　functionalized　WLS-PTA　adsorbent　exhibits　remarkable　SO2　adsorption　performance　(15.43　mmol/g),　exceptionally　high　selectivities　of　SO2/N2　(27522)　and　SO2/CO2　(6　5　2).　Surprisingly,　the　desulfurization　capacity　can　be　further　enhanced　by　the　positive　effect　of　the　water　vapor　co-fed.　It　is　unveiled　that　the　whole　SO2　adsorption　process　mainly　follows　the　dual　site　Langmuir-Freundlich　isotherm　model　and　Bangham　model.　This　work　sheds　light　on　the　design　of　polymer-solid　composite　adsorbents　for　selective　capture　of　SO2.　©　2024　Elsevier　B.V.