A new strategy has been successfully designed to synthesize curved ammonium copper molybdate [(NH4)(2)Cu( MoO4)(2)] nanoflakes on a copper surface by employing a novel solution-phase approach at room temperature. This method consists of a liquid-solid reaction between Na2MoO4 solution and the copper substrate itself in the assistance of formamide. The lamellar ammonium copper molybdate are approximately perpendicular to the copper substrate surface and are intermeshed with each other to form nanogroove structures. Formamide molecules cannot only promote the oxidation of copper substrate and the formation of copper complex, but also act as a NH4+ source in the final products. Furthermore, the selective adsorption of formamide molecules on different crystallographic planes of ammonium copper molybdate plays the major role in determining the curved morphology. In addition, using glucose as additives to control the nucleation and growth process (through a stepwise nucleation mechanism) can lead to a hierarchical sphere-like architecture.