A novel electrochemical sensor for capsaicin using mesoporous cellular foams (MCFs) as the sensitive material is reported. The surface morphology and electrochemical properties of the prepared MCFs modified carbon paste electrode (CPE) were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The proposed modified electrode shows high sensitivity towards the oxidation of capsaicin in 0.1 M perchloric acid solutions (pH 1.0). Under optimized conditions, the electrochemical oxidation current of capsaicin was found to be linearly related to the concentration over the range 0.76 to 11.65 μM with a correlation coefficient of 0.9990, and the detection limit was found to be 0.08 μM at a signal-to-noise ratio of 3. The proposed electrochemical sensor was successfully applied to the determination of capsaicin by using standard addition method with satisfactory results.