We unveiled superior base mediators for the annulative condensation of salicylaldehydes and acrylonitrile to give 3-cyano-2H-chromenes, which has been mediated only by 1,4-diazabicyclo[2.2.2]octane (DABCO) over the past two decades. The reactions were most efficiently mediated by 4-dimethylaminopyridine (DMAP), which yielded 3-cyano-2H-chromenes in higher yields than DABCO in most cases. We also confirmed that the reaction remained high yielding in a decagram-scale experiment with a catalytic amount of DMAP. The utility of this reaction was also exemplified by derivatization of an obtained 3-cyano-2Hchromene into a known 2H-chromene-3-carboxylic acid, which was previously synthesized with a nonreadily available reagent.