The chemical reactivity of 6‐methylchromone‐3‐carbonitrile (1) was studied towards some nucleophilic reagents. Reaction of carbonitrile 1 with malononitrile dimer and N′‐[(4‐methoxyphenyl)methylidene]‐2‐cyanoacetohydrazide (5) gave the unexpected chromeno[4,3‐b]pyridine 2 and benzoxocine‐3‐carbohydrazide 6, respectively. Reaction of carbonitrile 1 with 3‐amino‐1,2,4‐triazole, 2‐aminobenzimidazole, 7‐chloro‐4‐hydrazinoquinoline and 3‐hydrazino‐5,6‐diphenyl‐1,2,4‐triazine proceeds via γ‐pyrone ring opening followed by cycloaddition onto the nitrile function leading to a variety of heterocyclic systems. Structures of the new synthesized products were deduced on the basis of their analytical and spectral data.