Abstract. A nanostructured poly (o-toluidine)/silicon nanowires (NPOT/SiNWs) heterojunction has been fabricated with a low cost and simple techniques, where NPOT has been in situ polymerized upon SiNWs synthesized by chemical etching of a silicon wafer. The morphology of SiNWs before and after deposition of NPOT has been examined by scanning electron microscope (SEM). The chemical composition of NPOT has been investigated by Fourier transform infrared (FTIR), ultraviolet-visible (UV-visible) spectroscopy, and X-ray diffraction (XRD) techniques. NPOT morphology has also been examined by SEM before being deposited on the SiNWs. I-V measurements of the device have been made at room temperature under dark conditions. The heterojunction diode parameters such as turn-on voltage, reverse saturation current (I 0 ), ideality factor (η), barrier height (Φ B ) and series resistance (R s ) have been determined from the I − V curves using Schottky equations. The device shows promising characteristics as a candidate for producing heterojunction diodes. © The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its DOI.