Abstract: Polycyclic aromatic hydrocarbons (PAHs) are hazardous contaminants produced during the thermal processing of edible oils and have garnered extensive attention due to their potential carcinogenicity and adverse health impacts. Activated carbon is widely applied for PAHs removal by virtue of its well-developed pore structure and superior adsorption capacity. Nevertheless, the adsorption selectivity toward PAHs and the retention of beneficial lipid components remain poorly understood. In this study, peanut oil was used as a model system to elucidate the structure-activity relationship between the surface characteristics of activated carbon and PAHs adsorption behavior. The effects of particle size, pore structure, and surface oxygen-containing functional groups on PAHs removal efficiency and endogenous nutrient retention were systematically investigated. The results showed that reducing the particle size of activated carbon and increasing its specific surface area, total pore volume, and mesopore volume significantly improved PAHs removal performance, as improved pore accessibility and mass transfer efficiency contributed to enhanced adsorption. Pores ranging from 1.6 to 2.9 nm were identified as the dominant effective adsorption region for PAHs. This pore-size range closely matched the molecular dimensions of tocopherols (1.8-2.6 nm) but differed substantially from that of sterols (2.5-3.6 nm). Accordingly, the regulation of pore structure enables efficient PAHs removal while retaining sterols, although partial tocopherol loss may occur simultaneously due to competitive adsorption. Furthermore, the introduction of oxygen-containing functional groups (—OH, —COOH, and CFY=,1O) on activated carbon surfaces improved the adsorption stability of PAHs, with adsorption energies ranging from -0.911 to -0.866 eV. Surface functionalization facilitated the preferential adsorption of PAHs and mitigated tocopherols adsorption loss (-0.909 to -0.598 eV) but increased the nonspecific adsorption of sterols (-1.031 to -0.908 eV). Overall, pore structure and surface chemistry synergistically regulate the adsorption selectivity and nutrient retention of edible oil. This study provides a theoretical basis for the rational design and screening of highly selective adsorbents for PAHs purification in edible oils.