This paper describes a simple complex-surfactant-assisted hydrothermal reduction approach to the facile synthesis of metal copper nanowires with average diameters of ∼85 nm and lengths of several tens of micrometers. These copper nanowires were formed through the reduction of the CuII−glycerol complexes (Cu(C3H6O3)) by phosphite (HPO32-) in the presence of surfactant sodium dodecyl benzenesulfonate (SDBS) at 120 °C. High-resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED) indicate that the resulted nanowires had preferred [110] growth direction. The formation mechanism for Cu nanowires had been properly proposed. Some influencing factors on the morphologies of the final products had also been discussed.