Silica supported sulfuric acid (SSA) has been demonstrated to be capable of effectively removing phenyl VOCs through the reaction-type adsorption mechanism. The effects of the solvent (water, ethyl acetate) used to impregnate silica gel with H2SO4 solution in order to prepare SSA adsorbents have been studied. As-prepared two series SSA(E)-x and SSA(W)-x materials (x = 1, 2, 3, 4) were characterized by TG, SEM/EDS and N2 adsorption/desorption techniques, and their breakthrough adsorption performances were evaluated from experimental and theoretical aspects. The results showed that the H2SO4 loading amounts were 2.8, 4.0, 4.8 and 5.6 mmol g−1 respectively for both SSA(E)-x and SSA(W)-x when x equaled 1, 2, 3, 4. Among them, SSA(E)-4 was found to have a higher proportion of the C-state H2SO4 than SSA(W)-4. Both SSA(E)-x and SSA(W)-x exhibited significant removal capacity of gaseous o-xylene. The reactive temperature regions were determined to be 120–170 °C for SSA(E)-4 and 120–160 °C for SSA(W)-4 with a common optimum point of 160 °C. Both SSA(E)-x and SSA(W)-x adsorbents exhibited excellent recyclability and reuse performance. Further, the series SSA(E)-x materials outperformed the series SSA(W)-x on all adsorption performance metrics, suggesting that ethyl acetate is a preferred solvent for preparing the SSA materials in phenyl VOCs removal application.