Abstract The one‐pot construction of diversified sulfonyl flavones was developed by K 2 CO 3 ‐mediated formal (5+1) stepwise annulation of α‐sulfonyl o ‐hydroxyacetophenones with substituted nitriles under the open‐flask atmosphere conditions. A plausible mechanism is proposed and discussed. This method provides intermolecular and intramolecular ring‐closure via the formations of one carbon‐oxygen single (C−O) bond, one carbon‐carbon (C=C) double bond, and the cleavage of one carbon‐nitrile triple (C≡N) bond.