A facile and reproducible approach was reported to synthesize nanoparticle-attached SnO nanoflowers via decomposition of an intermediate product Sn6O4(OH)4. Sn6O4(OH)4 formed after introducing water into the traditional nonaqueous reaction, and then decomposed to SnO nanoflowers with the help of free metal cations, such as Sn2+, Fe2+, and Mn2+. This free cation-induced formation process was found independent of the nature of the surface ligand. It was demonstrated further that the as-prepared SnO nanoflowers could be utilized as good anode materials for lithium ion rechargeable batteries with a high capacity of around 800 mA h g(-1), close to the theoretical value (875 mA h g(-1)).