The use of square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode (Hg(Ag)FE) for the analytical determination of ambazone in urine samples and pharmaceutical formulations is described. A single reduction peak in Britton-Robinson buffer at pH 4.0 was detected at about −1.4 V versus Ag/AgCl. Mechanistic studies have shown that the compound can act as an electrocatalyst. The method was validated. The analytical curve was linear in the concentration range from 1.0×10−9 to 1.0×10−7 mol L−1. The detection and quantification limits were found to be 3.0×10−10 mol L−1 and 1.0×10−9 mol L−1, respectively. The proposed method was successfully applied to ambazone determination in real samples.