<p>The development of porous carbon materials (PCM) for the efficient adsorption of volatile organic compounds (VOCs) emitted by the petrochemical industry such as light alkane and aromatic compounds remains a big challenge. The doping of non-metal hetero atoms provides an effective method to construct functional groups on the surface of PCM in order to enhance the electrostatic interaction between VOCs and the carbon adsorbent. In this study, carbon aerogels doped by phosphorus with tailored pore structures were prepared, and they exhibit enhanced adsorption performance for light alkane and aromatic compounds, which was also validated by pilot test in a petrochemical plant. The adsorption mechanism was elucidated through a combination of the structural characterization, kinetic analysis and theory calculations. It reveals that the treatment of phosphoric acid induces pore structure evolution of carbon aerogels, and the surface functional group of C–O–P–O(OH)₂ becomes more prevalent than that of C–P–O(OH)₂ as the doping amount of phosphorus increases. The adsorption of ethane and propane is dominated by the physisorption, respectively, whereas the adsorption of butane and benzene occurs more easily according to the chemisorption due to the formation of C–O–P–O(OH)₂ groups. This study provides a fundamental insight for the rational design of efficient carbon-based adsorbents for VOCs abatement.</p>