The electrochemical and interfacial adsorptive behavior of pipazethate HCl (PZ.HCl) onto the developed carbon paste electrode surface modified with sodium-montmorillonite clay (Na-MMT CPE) were investigated using cyclic voltammetry. Two validated adsorptive anodic stripping voltammetry methods have also been developed for its determination using 7 % (w/w) Na-MMT-modified CPE. Langmuir isotherm can describe the experimental data well, indicating monolayer adsorption. Limits of detection of 2.4 × 10−7 and 3.0 × 10−8 mol L−1 PZ.HCl were achieved in the bulk form using linear-sweep and square-wave adsorptive anodic stripping voltammetric methods, respectively. The developed methods were also successfully applied for determination of PZ.HCl in pharmaceutical formulation and in spiked human serum without time-consuming extraction steps prior to the analysis. Statistical comparison of the results of the proposed methods with that of official and reported spectrophotometric methods indicates no significant difference in precision and accuracy between the proposed and reference methods.