Herein, by screening 89 porous materials (metal-organic frameworks and covalent organic frameworks), the ultradeep desulfurization from model gasolines was investigated by the facile adsorptive approach by grand canonical Monte Carlo simulations. The accessible surface area and void fraction ratio of porous materials are of great significance for the ultradeep desulfurization of gasoline. ZnBDC, MOF-70, MOF-69C, UIO-66, Cd3BTB2, ZIF-77, ZIF-69, and ZIF-2 are identified with ultrahigh selectivity for thiophene/n-octane systems at 298 K and 10 kPa. The relationship between the loading amount of thiophene in materials and the difference of isosteric heat of thiophene and n-octane (or benzene) was confirmed. The pressure swing adsorption and temperature swing adsorption are considered to mimic the separation in industrial processes. Functionalization (impregnation) is an efficient route to boost the selectivity of removal of sulfur-containing compounds from gasoline. Adsorption and separation mechanisms for thiophene from gasolines are determined by the composition and inner structure of materials.