A metal/additive‐free, TBHP‐promoted synthesis of 12H‐Chromeno[2,3‐b]quinolin‐12‐ones from 2‐phenoloxyquinolinyl‐3‐carboxaldehydes has been described via cross‐dehydrogenative coupling of aldehydic C−H bond with arene C−H bond in good to excellent yields. Reaction could be extended to the synthesis of Chromeno[2,3‐c]pyrazol‐4(1H)‐ones, 3‐Phenyl‐5H‐chromeno[2,3‐b]pyridin‐5‐ones and Xanthone respectively.