In this work, piroxicam concentration measurements in pharmaceutical products and real samples were carried out using glassy carbon electrode modified with copper nanoparticles. The CuNPs/GCE has a high sensitivity, fast response and suitability lifetime in respect to electro-oxidation and determination of piroxicam. The electro-oxidation of piroxicam showed dependency on the pH changes (3–8) of supporting electrolyte, and pH 7 was selected as an optimum value. The behavior of fabricated modified electrode was checked as a sensitive detection method for determination of piroxicam using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Under optimal conditions, DPV technique was used for determination of piroxicam within 3 to 135 μm by modified electrode with a low detection limit of 0.22 μm (for S/N = 3) and sensitivity of about 0.061 μA μm−1 m−2 . The determination of piroxicam in pharmaceutical products without any interference of excipients in the formulations and foreigner species in real samples, resulted in an acceptable deviation from the mentioned concentrations.