We have developed a peracetic acid (PAA) sensor based on a polybenzimidazole-modified gold (PBI/Au) electrode. Fourier transform infrared and X-ray photoelectron spectroscopy indicated that PAA oxidized 69.4% of the imine in PBI to form PSI N-oxide, increasing the electrochemical reduction current during cyclic voltammetry. The chemical oxidation of the PBI/Au electrode by PAA, followed by its electrochemical reduction, allowed PAA to be detected directly and consecutively by assessing its reduction current. The PAA sensor had a broad linear detection range (3.1 mu M-1.5 mM) and a rapid response time (3.9 s) at an applied potential of -0.3 V. Potentially interfering substances, such as hydrogen peroxide, acetic acid, and oxygen, had no effect on the ability of the probe to detect PM, indicating high selectivity of the probe. Furthermore, the detection range, response time, and sensitivity of the sensor could all be improved by modification of the smooth planar electrode surface to a porous three-dimensional configuration. When compared to the analytical characteristics of other PAA sensors operating under optimal conditions, the three-dimensional PBI/Au electrode offers a rapid detection time, a usable linear range, and a relatively low detection limit. (C) 2011 Elsevier Ltd. All rights reserved.