Nitrogen-rich　hollow　carbon　microspheres　were　successfully　synthesized　using　resorcinol　and　formaldehyde　as　carbon　sources,　tetraethylenepentamine　(TEPA)　as　a　catalyst,　and　nitrogen　source,　with　SiO2　microspheres　as　a　hollow　template.　The　hollow　carbon　microspheres　were　prepared　by　adding　varying　amounts　of　SiO2　hollow　templates　to　a　fixed　amount　of　TEPA.　The　shell　thickness　increased　as　the　amount　of　SiO2　template　decreased　and　the　shell　thicknesses　of　AHMCS-2(1),　AHMCS-2(3),　and　AHMCS-2(5)　were　28.5　nm,　17.3　nm,　and　12.7　nm,　respectively.　The　activated　hollow　carbon　microspheres　(AHMCS-2(1),　AHMCS-2(3)　and　AHMCS-2(5))　contained　4.66%,　5.05%,　and　3.27%　nitrogen,　respectively.　Due　to　the　sufficient　activation　process,　the　specific　surface　area　and　microporous　volume　of　hollow　carbon　microspheres　are　greatly　increased　compared　to　solid　carbon　microspheres,　therefore,　their　CO2　adsorption　performance　is　superior　as　well.　As　the　shell　layer　thickens,　the　specific　surface　area　and　micropore　volume　of　the　activated　hollow　carbon　microspheres　increased,　among　which　AHMCS-2(1)　showed　the　largest　specific　surface　area　and　micropore　volume　of　1146　m2/g　and　0.45　cm3/g,　respectively.　Similarly,　the　CO2　adsorption　capacity　of　activated　hollow　carbon　microspheres　increased　with　the　increasing　thickness　of　the　shell　layer,　and　that　of　AHMCS-2(1)　reached　5.54　mmol/g　at　0　°C.　High　specific　surface　area,　high　micropore　volume,　high　nitrogen　content,　and　small　micropore　pore　size　are　favorable　for　CO2　adsorption　by　carbon　microspheres.　The　hollow　carbon　microspheres　exhibit　high　CO2　dynamic　adsorption　capacity,　excellent　selective　adsorption,　and　good　cyclic　stability.　Graphical　Abstract:　(Figure　presented.).　©　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature　2024.