In this article, we focus on the introduction of nitroarene as an alternative electrophile for C_aryl–O cross-coupling chemistry. In polar aprotic solvents and in the presence of a base at elevated temperature nitroarene undergoes cross-coupling with arylboronic acids or phenols under metal or metal-free reaction conditions. Compared to the conventional aryl halides, nitroarene provides highly attractive and environmentally friendly options for the synthesis of diaryl ether derivatives.