Vertically aligned p-type silicon nanowire (SiNW) arrays were fabricated through metal-assisted chemical etching (MACE) of Si wafers. An indium tin oxide/indium zinc oxide/silicon nanowire (ITO/IZO/SiNW) heterojunction diode was formed by depositing ITO and IZO thin films on the vertically aligned SiNW arrays. The structural and electrical properties of the resulting ITO/IZO/SiNW heterojunction diode were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and current−voltage (I−V) measurements. Nonlinear and rectifying I−V properties confirmed that a heterojunction diode was successfully formed in the ITO/IZO/SiNW structure. The diode had a well-defined rectifying behavior, with a rectification ratio of 550.7 at 3 V and a turn-on voltage of 2.53 V under dark conditions.