Reducing the poisoning effect of alkali and heavy metals over ammonia selective catalytic reduction (NH3-SCR) catalysts is still an intractable issue, as the presence of K and Pb in fly ash greatly hampers their catalytic activity by impairing the acidity and affecting the redox properties of the catalysts, leading to the reduction in the lifetime of SCR catalysts. To address this issue, we propose a novel self-protected antipoisoning mechanism by designing SO42-/TiO2 superacid supported CeO2-SnO2 catalysts. Owing to the synergistic effect between CeO2 and SnO2 and the strong acidity originating from the SO42-/TiO2 superacid, the catalysts show superior catalytic activity over a wide temperature range (240-510 °C). Moreover, when K or/and Pb are deposited on SO42-/TiO2 catalysts, the bond effect between SO42- and Ti-O would be broken so that the sulfate in the bulk of SO42-/TiO2 superacid support would be induced to migrate to the surface to bond with K and Pb, thus prohibiting poisons from attacking the Ce-Sn active sites, and significantly boosting the resistance. Hopefully, this novel self-protection mechanism derived from the migration of sulfate in the SO42-/TiO2 superacid to resist alkali and heavy metals provides a new avenue for designing novel catalysts with outstanding resistance to alkali and heavy metals.