he effects of surfactant on the voltammetric behavior of doxycycline (DOC) were investigated using conductive carbon black paste electrode (CCBPE) as working electrode. A new electrochemical method for determining DOC in aqueous solution was developed with the help of surfactant. The electrostatic interaction between the DOC molecules and the sodium dodecyl benzene sulfonate (SDBS) by self-assembled on the surface of CCBPE promoted the accumulation of the analyte. In B-R buffer solution of pH 2.0, the presence of 2.0×10–4 mol/L SDBS significantly improved the sensitivity of detection of DOC. In the presence of SDBS, the voltammetric behavior of DOC was investigated by cyclic voltammetry. An irreversible and adsorption-controlled electrode reaction occurs with 1 proton and 2 electrons participation. Under the optimum conditions, the anodic peak current of DOC is proportional to its concentration in the range of 1.0×10–7−2.3×10–5 mol/L with a detection limit of 4.5×10–8 mol/L (S/N=3). Inorganic ions do not have negative effects on the determination, while organic molecules have positive effects probably due to the competitive adsorption function. The average recoveries in the range of 97.44%−105.28% were obtained. Thus, the developed method for the determination of DOC possesses advantages such as simple operation, fast response, low detection limitation, good recovery, and repeatability.