Thermal decomposition of Co(acac)(3) and Cu(acac)(2) in benzylamine leads to the formation of [100] directed Cu-doped h-CoO nanorods, which are very stable in an aqueous solution. The formation mechanism of the [100] directed Cu-doped h-CoO nanorods is fully elucidated by using first-principles calculations, demonstrating that Cu-doping not only changes the growth direction but also enhances the stability of the nanorods significantly. Evaluation of the electrochemical performance of Cu-doped h-CoO nanorods shows high initial Coulombic efficiency and ultrahigh capacity with excellent cycling performance, indicating their suitability as an anode material for next generation lithium-ion batteries.