This study reports a sensitive electro-analytical method for the determination of trace amounts of Cu2+ using a phytate functionalized polypyrrole nanowires (PPy NWs) modified glass carbon electrode. The phytic acid/polypyrrole (PA/PPy) NWs were prepared by an electrostatic adsorption and ultrasonic mixing. The results showed that both PPy NWs and PA/PPy NWs modified glassy carbon electrodes have electrochemical responses toward Cu2+. However, owing to the synergistic contribution between the PPy NWs and PA, the PA/PPy NWs modified electrode exhibited higher sensitivity than that of PPy NWs modified electrode. The PA/PPy NWs composites functionalized electrodes showed a good linear relationship with Cu2+ at concentration ranges of 10–60μg·L−1, and the limit of detection (S/N=3) was 3.33μg·L−1. In addition, the electrochemical sensor was applied to assay Cu2+ in real water samples.