Electrochemical modification of carbon-paste electrode (CPEs) by silver particles and its applicability for electroanalytical determination of 4-nitroaniline (4-NA) were reported in this study. Electrochemical surface modification was performed by cyclic voltammetry within the range from 600 to − 400 mV in solution containing 0.5 mmol L −1 AgNO 3 dissolved in 0.1 mol L −1 of KNO 3 at the scan rate of 10 mV s −1 by applying 1.5 cycles (six segments). Silver particles deposited onto surface of carbon-paste electrode (Ag-CPE) were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The proposed catalyst exhibits remarkably an electro-catalytic performance toward 4-nitroaniline reduction. The catalytic peak current obtained by differential pulse voltammetry (DPV) was linearly dependent on the 4-NA concentration over the range of 8.0 × 10 −8 to 1.0 × 10 −4  mol L −1 with a detection limit of 4.18 × 10 −8  mol L −1 . The proposed sensor was successfully applied for 4-nitroaniline determination in drinking water samples.