A new method for the determination of 4-nitrophenol(4-NP) by differential pulse voltammetry (DPV) based on adsorptive stripping technique was described. Cyclic voltammetry (CV) and linear scan voltammetry (LSV) were used in a comparative investigation into the electrochemical reduction of 4-NP at a Na-montmorillonite(SWy-2) and anthraquione (AQ) modified glassy carbon electrode. With this chemically modified electrode, 4-NP was first irreversibly reduced from φNO₂ to φNHOH at −0.78 V. A couple of well-defined redox peaks at +0.22 V (vs. SCE) were responsible for a two-electron redox peak between φNHOH and φNO. Studies on the effect of pH on the peak height and peak potential were carried out over the pH range 2.0–9.0 with the phosphate buffer solution. A pH of 3.4 was chosen as the optimum pH. The other experimental parameters, such as film thickness, accumulation time and potential etc. were optimized. Anodic peak currents were found to be linearly related to concentration of 4-NP over the range 0.3–45 mg l⁻¹, with a detection limit of 0.02 mg l⁻¹. The interference of organic and inorganic species on the voltammetric response have been studied. This modified electrode can be used to the determination of 4-NP in water samples.