This work presents, for the first time, the voltammetric behavior of clonidine (CLO) drug and its determination, using an unmodified glassy carbon electrode (GCE). CLO exhibited only an irreversible oxidation process on the GCE, with peak potential at +0.85 V in pH 12 (vs Ag/AgCl). CLO oxidation process is pH‐dependent and the electrochemical mechanisms on the GCE were proposed in acidic and basic medium. The determination of CLO was optimized in 0.1 mol L−1 phosphate buffer solution at pH 12.0 using differential pulse voltammetry (DPV), which provides a good linear range (0.65 to 106.00 μmol L−1) and low theoretical limit of detection (0.14 μmol L−1) for the quality control of this drug in pharmaceutical samples. In addition, stable responses of CLO at the GCE were obtained in the same day (RSD = 3.4 %; n = 5) and different days (RSD = 2.0 %; n = 3). Moreover, the determination of CLO in a pharmaceutical formulation using the proposed GCE‐DPV method presented good accuracy, since the recovery was close to 100 % and the dosing result was in agreement with an official method (HPLC‐UV). The proposed method demonstrates a good analytical performance for CLO determination in pharmaceutical samples, providing a faster, simpler and lower‐cost alternative for quality control of CLO than other reported methods.
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