The electrochemical behaviors of estrone in the presence of various surfactants were examined with great details. It is found that a cationic surfactant, cetyltrimethylammonium bromide (CTAB), obviously facilitates the electro-oxidation of estrone at carbon paste electrode (CPE) from the significant peak current enhancement and the negative shift of peak potential. Additionally, chronocoulometry and electrochemical impedance spectroscopy (EIS) were also used for further investigation of the electrode process of estrone, indicating that low concentration of CTAB exhibits excellent enhancement effects on the electrochemical oxidation of estrone, greatly enhances the diffusion coefficient and the electron transfer rate. Based on this, an electrochemical method was proposed for the determination of estrone. The oxidation peak current is proportional to the concentration of estrone in the ranges over 9.0 × 10?8 - 8.0 × 10?6 mol/L, and a low detection limit of 4.0 × 10?8 mol/L was obtained for 180s accumulation at open circuit (S/N = 3). Finally, this proposed method was demonstrated using estrone tablets with good satisfaction.