CoSb3 nanowire arrays, preferred orientation of [510], were fabricated by electrodeposition of Co2+ and Sb3+ into anodic aluminum oxide (AAO) templates. The morphologies, structure, and composition of the as-synthesized sample have been performed using X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy-dispersive X-ray spectroscopy (EDS). Based on the previous investigation on CoSb3 nanowire arrays orientated along [420], the formation mechanism for different preferential orientation nanowire arrays was discussed.