The degradation of nitrobenzene by synchronistic oxidation and reduction was investigated using an internal circulation microelectrolysis (ICE) reactor with an active volume of 0.018 m(3). Compared with a conventional fixed bed reactor with and without aeration, the ICE reactor exhibited a markedly higher nitrobenzene degradation efficiency. The effects of various operational parameters such as reaction time, aeration rate, initial nitrobenzene concentration, initial pH, and a volume ratio of iron and carbon (Fe/C) were also investigated. The optimal operating conditions (reaction time = 60 min, aeration rate = 5 x 10(-4) m(3)/s, initial concentration of nitrobenzene = 300 mg/L, pH = 3.0, Fe/C = 1:1) gave removal efficiencies of nitrobenzene and chemical oxygen demand of 98.2% and 58%, respectively. The biodegradability index of the treated nitrobenzene solution was 0.45, which is 22 times that of the original solution. The reaction intermediates were identified through high-performance liquid chromatography, ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry, and ion chromatography. The primary intermediates were determined to be aniline, phenol, and carboxylic acids, indicating that nitrobenzene was synchronously oxidized and reduced in the ICE reactor. Based on the identified intermediates, a possible pathway for nitrobenzene degradation in the ICE reactor is proposed.