The performance of adsorbents plays a critical role in the adsorption of gasoline vapor mixtures. Therefore, this paper systematically characterized the pore structure information of three kinds of silica gels, gel-A, gel-B and gel-C. The standard adsorption energies were calculated, and the performance of the first passivation adsorption and dynamic adsorption were also investigated. The experimental results showed that gel-A is rich in microporous area, however, gel-B and gel-B exhibit obvious mesoporous character. The standard adsorption energy calculated can also reveal the microporous distribution of the three silica gels. In addition, the adsorbed capacity of first passivation and dynamic adsorption shows the same trend, gel-A > gel-B > gel-C. Gasoline vapor adsorption on silica gels was determined by microporous distribution, thus affecting the corresponding adsorption capacity.