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Selective catalytic reduction of NO x with ammonia (NH 3 -SCR) under the exposure of multiple poisons in fly ash remains a great challenging issue for environmental protection. Herein, the intelligently self-tunable defense effects of Ce(SO 4) 2 additive modification for the V 2 O 5 /CeO 2 catalyst with excellent resistance against K and Zn co-poisoning was originally illustrated. The Ce(SO 4) 2 additive could firstly act as an inhibitor to certainly restrain the electron transfer between V and Ce species to decrease the redox property, but the high NO x reduction efficiency of Ce(SO 4) 2 modified fresh catalyst could be maintained due to the enhancement of vanadium species polymerization and acidity. Unexpectedly, the Ce(SO 4) 2 additive would smartly translate to act as a promoter over the co-poisoned catalyst to effectively combine with poisons, thus releasing most active vanadium species to exhibit superior co-poisoning resistance to K and Zn. This work provides a novel self-tunable multi-poisoning-resistant strategy via acid additive modification for SCR catalysts. [Display omitted] • Ce(SO 4) 2 modified vanadia catalyst was obtained to fight K and Zn co-poisoning. • Ce(SO 4) 2 modification greatly improved NO x conversion and co-poisoning resistance. • Ce(SO 4) 2 was inhibitor to restrain electron transfer between active V and Ce sites. • Ce(SO 4) 2 translates to promoter to fix K and Zn poisons among poisoned catalysts. [ABSTRACT FROM AUTHOR]