parts, or reducing the anionic charge (QAnion); their correlations follow QO≈IFCCN>SDN>SDO>QAnion. The reactivities of catalysts with ionic-pair substituents could be largely improved compared with those of conventional counterparts; most of them could be comparable to or higher than those of known efficient organocatalysts. A linear correlation between the Hammett constants of ionic-pair substituents and the reactivities of catalysts was established. Changing the anion, rather than changing the cation, should be a more powerful way to increase the reactivity, and the multiple ionic-pair substituent effects would be superior to single ones. The appropriate NOH bond strengths of these catalysts are responsible for their good catalytic performances.