Improvement of methods for the detection of an analyte at a low concentration with high sensitivity has become an important point of interest. An effort has been made to know the electrochemical behavior of chlorpheniramine maleate in the presence of an anionic surfactant. Voltammograms were obtained in the range of 6.0–11.2 pH, and the maximum peak current (IP) was observed at pH 10.4. Various physicochemical parameters were estimated, including the process on the surface of the electrode, which was found to be diffusion controlled, heterogeneous rate constant, number of electrons transferred, and charge transfer coefficient. Square wave voltammetry of chlorpheniramine maleate at the modified electrode exhibited a linear calibration curve in the concentration range of 1.0–100 μmol/L, with a limit of detection of 28 nmol/L. The proposed technique was successfully used for the determination of chlorpheniramine maleate in pharmaceuticals, as well as in biological samples.