Electrosorption-enhanced solid-phase microextraction (EE-SPME) based on activated carbon fiber (ACF) was developed for determination of aniline in aqueous solution. A porous ACF, served as working electrode in electrosorption procedure, was prepared and attached to a commercial manual SPME device. Parameters affecting the adsorption efficiency were investigated. Under optimized condition, whichwas 400mVelectrosorption potential, 0.01M Na2SO4 electrolyte, pH 7, and electrosorption at 40℃ for 10min, the method exhibited wide linear range (0.1-100gL−1, R2=0.9980), good repeatability of adsorption (RSD 6.15%, n=6), and low detection limit (0.02 gL−1). The feasibility of the method was evaluated by analyzing lake water spiked with aniline. Comparison was made with direct immersion (DI) ACF-SPME without electrosorption enhancement. The proposed procedure was demonstrated to be a simple, fast, sensitive sample preparation method for determination of aniline in water samples.