The roll-up effect occurs as a result of the displacement of SO2 with H2O(g) when sulfur dioxide from humid flue gas is adsorbed by zeolites. It is mainly affected by SiO2/Al2O3 ratio (S/A) of zeolites, despite lack of detailed studies on use of hydrophilic zeolite. In this study, two zeolites of FAU 13X (S/A of 1.77) and LTA 5A (S/A of 1.51) were used to explore their roll-up effects using the breakthrough curve method. It is shown that the zeolite structure significantly influences the roll-up effect. The roll-up effect of FAU 13X is more significant than that of LTA 5A at the same water vapor content. The maximum roll-up ratio (η) for LTA 5A and FAU 13X are, respectively, 1.23 and 2.55 within the water vapor content range of 0.9–2.4%. Moreover, η of FAU 13X tends to decrease more rapidly than that of LTA 5A with increasing temperature or decreasing adsorption gas pressure. The presence of oxygen inhibits the roll-up effect and increases the breakthrough time of SO2. For the acid-modified zeolite, there is a positive correlation between η and concentration of Ca2+ or Na+ on zeolite surface, indicating obvious impact of cations on the roll-up effect.