An innovative method for the determination of isoniazid tablets is studied through electrochemical method for the modification of glassy carbon electrode (GCE). Polyoxomolybdate, with stable structures, has not been widely used for the determination of substance. In this study, the mentioned polyoxomolybdate was characterized by Fourier transform infrared spectroscopy (FT-IR), UV-vis, X-ray diffraction (XRD), Atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS), and used to modify the glassy carbon electrode. The electrochemical performance of the polyoxomolybdate@GCE was investigated with cyclic voltammetry (CV) and differential pulse voltammetry (DPV), compared with the unmodified electrode, the proposed polyoxomolybdate modified electrode exhibited strong electro-catalytic activities towards isoniazid (INH). Under the optimized conditions, there was linear relationships between the DPV peak currents and the concentrations in the range of 1 × 10 -7 g/L to 3 × 10 -7 g/L for INH (R 2 = 0.9979), with the limit of detection (LOD) of 0.024 μg/L (based on S/N = 3). The modified electrode has proper reproducibility (RSD < 5%), stability, response time (< 3 min) and lifetime (up to 6 days).