Amine-containing solids are promising adsorbents for CO2 capture, but they suffer from irreversible poisoning by the highly acidic SO2 in flue gas. Here, we demonstrate a facile strategy to inhibit SO2 poisoning. We first prepared an amine-containing adsorbent by impregnating polyethyleneimine (PEI) into porous silica. The PEI located at the external surface of the adsorbent was selectively alkylated with epoxide so that amines were fully converted to tertiary amines. As opposed to that onto primary and secondary amines, SO2 adsorption onto tertiary amines is fully reversible. Therefore, during the flue gas adsorption, SO2 is reversibly captured by the tertiary-amine-rich layer and then desulfurized CO2 is adsorbed onto PEI beneath this layer. The resultant adsorbent showed insignificant loss of CO2 adsorption capacity (8.52%) even after 1000 CO2 adsorption-desorption cycles in the presence of SO ppm SO2, whereas conventional PEI/silica showed severe capacity loss (65.1%) due to irreversible SO2 poisoning.