Synthesis of 2‐aminofuran derivatives with an azulene or N,N‐dimethylanilino substituent was established by the formal [2+2] cycloaddition–retroelectrocyclization of 3‐(1‐azulenyl or N,N‐dimethylanilino)‐2‐propyn‐1‐ols with tetracyanoethylene, followed by intramolecular nucleophilic addition to the initially formed tetracyanobutadiene moiety of the internal hydroxyl group that come from 2‐propyn‐1‐ol. The reaction proceeds under mild conditions with short reaction period. The products of the reaction are readily available through a simple purification procedure. 2‐Aminofuran derivatives obtained by this reaction could be converted into 6‐aminofulvene derivatives upon reaction with various amines. The structures of 2‐aminofuran and 6‐aminopentafulvene with a N,N‐dimethylanilino substituent were confirmed by single‐crystal X‐ray structural analysis.