For the first time, copper nanowires / poly (naphtoquinone Chromium (III)) (Cu NWs - poly NQ-Cr(III)) was synthesized through oxidative polymerization of naphthalene-2,3-diol (2,3DHN) by sodium dichromate (Na2Cr2O7) in the presence of copper nanowires. The poly (naphtoquinone Chromium (III)) was characterized by various techniques including, field emission scanning electron microscope (FESEM), energy dispersive spectroscopy (EDS), ultraviolet–visible (UV–Vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, Thermogravimetric analysis, differential scanning calorimetry (TGA /DSC), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Results of these tests confirmed the formation of 30–90 nm thick poly NQ-Cr(III) layer on the copper nanowires. Then, Cu NWs - poly NQ-Cr(III) was applied for the modification of carbon paste electrode (CPE/ (Cu NWs - poly NQ-Cr(III)) for simultaneous voltammetric detection of para-Aminophenol (para-AP), Phenol and para-Nitrophenol (para-NP). The sensor exhibited low detection limits (LOD) of 0.05, 0.2 and 0.7 µM for para-AP, Ph and para-NP, respectively. The responses were linear for para -AP at the concentration ranges of 0.6–3.0 and 3.0–260 µM, for Ph at the concentration ranges of 1.0–5.5 and 5.5–150.0 µM and for para -NP at the concentration ranges of 2.0–9.0 and 9.0–210.0 µM. Eventually, the modified electrode showed very good practical utility to detect para-AP, Ph and para-NP in tap and river water samples.