4-nitrophenol (4-NP) is considered to be a harmful solid waste because of its toxicity and persistence. It is categorised as a priority contaminant by the United States environmental protection agency. In this work, we present a simple, easy and comprehensive electrochemical investigation of the electrocatalytic reduction of 4-NP in Britton-Robinson buffer solution as the supporting electrolyte at the surface of zero-valent silver electrode (ZVAgE). Different electrochemical methods such as cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, and Tafel plots were used to evaluate heterogeneous kinetics and illustrate the reduction mechanism of 4-NP. The experimentally determined parameters confirm that ZVAgE has a significant electrocatalytic activity towards 4-NP electro-reduction as compared to glassy carbon electrode (GCE). Under optimal conditions, the detection of 4-NP was found to have a low detection limit of 3.03 × 10 −7 mol L −1 in the range from 8.0 × 10 −6 to 1.0 × 10 −4 mol L −1 . Additionally, the sensor was successfully applied in the determination of 4-NP even in the presence of other common electroactive interference and real samples analysis (wastewater and river water samples). Therefore, the proposed method is simple, rapid, stable, sensitive, specific, and cost-effective and can be applicable for real sample detection.