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In this paper, a highly sensitive and selective method based on the poly (sulfosalicylic acid) modified electrode (PSA /CPE) to detect phenol was established. The morphologies and interface properties of PSA film were characterized by scanning electron microscopy and electrochemical impedance spectroscopy. It was illustrated that the PSA/CPE had an excellent electrocatalytic ability towards the oxidation of phenol. Meanwhile the influence of parameters such as pH and scan rate effect on the analytical performance of the sensor was evaluated. Moreover, the interference from o-nitrophenol can be neglected. By using differential pulse voltammetry (DPV), linear calibration curves were obtained as 5–175 and 220–555 μmol L−1 for phenol. The detection limits are 2.2 μmol L−1 for phenol. With favorable selectivity and sensitivity, the present method has been applied to the determination of phenol in oilfield wastewater.