Adsorptive　desulfurization　is　an　effective　technology　for　removing　aromatic　sulfur-containing　compounds　from　liquid　hydrocarbon　fuels,　but　the　existing　adsorbents　have　poor　adsorption　performance　and　stability.　Herein,　P,　N-co-doped　metal-free　3D　porous　carbon　was　first　prepared　by　ZiF-8　and　applied　in　adsorptive　desulfurization.　The　incorporation　of　P　and　N　heteroatoms　changes　the　surface　chemistry　of　the　carbon　skeleton,　meanwhile,　the　P　doping　effectively　adjusts　the　pore　structure　of　the　adsorbents.　Accordingly,　the　P-NPC-1000　exhibited　a　remarkable　adsorption　capacity　of　60.16　mg　S/g　for　dibenzothiophene　(DBT),　with　a　32%　increase　in　adsorption　capacity　compared　to　solely　N-doped　carbon　(45.41　mg　S/g).　It　also　demonstrated　excellent　reusability　with　adsorption　capacity　from　54.22　to　48.14　mg　S/g　after　6　cycles.　The　Langmuir　and　the　pseudo-second-order　kinetic　models　presented　best　fitting　results　for　DBT　adsorbing　on　the　P-NPC-1000.　Moreover,　the　adsorption　mechanism　was　further　investigated　through　DFT　calculations　and　special　adsorption　experiments.　It　was　proved　that　the　P-and　N-sites　cooperate　synergistically　to　enhance　the　interaction　between　P,　N-co-doped　carbon　and　DBT.　The　acid-base　interaction　and　polar　interaction　between　P-/N-sites　and　DBT,　together　with　the　pore　structure,　make　the　P-NPC-1000　highly　promising　in　adsorptive　desulfurization.