Coal fly ash (CFA) is an alternative carrier of selective catalytic reduction (SCR) catalyst, but its reactivity is usually poor. Herein, the alkali-acid combined activation was proposed to prepare the CFA-supported high-temperature SCR catalyst. The results revealed that 1.2 g/gCFA of NaOH and 0.6 g/gCFA of H2SO4 was the optimal CFA activation condition. The NaOH first destroyed the quartz crystal over the CFA, generating the Si-OH groups. Subsequently, H2SO4 enhanced the extraction of aluminates and enriched the acid sites, which promoted the standard SCR. Besides, the generated porous fragments facilitated the dispersion of Fe3+ species and improved the fast SCR.