A single-factor experiment was designed to investigate the effects of the pH, Fe0 dosage, persulfate(PS) dosage and tetracycline(TC) initial mass concentration on the TC removal rate to explore the optimum conditions for the Fe0/PS system to degrade TC. Using the results of single factor test and pseudo first-order kinetic model, the reaction order of the influencing factors of TC degradation in Fe0/PS system was obtained. The types of free radicals in Fe0/PS system were determined by free radical quenching test. The degradation products and pathways of TC in Fe0/PS system were studied by liquid chromatography-mass spectrometry. The results showed that when the initial mass concentration of 30 mg/L TC, the pH 3.0, at the dosage of PS 2.0 mmol/L, the dosage of Fe0 1.00 mmol/L and 25 ℃ temperature, the removal rate of TC reached 94.11% after 45 min. The reaction orders of PS dosage, Fe0 dosage and TC concentration were 0.93, 0.89 and -0.78, respectively;?OH and SO–4? were involved in the degradation of TC, in which SO–4? played a major role. TC was effectively degraded in Fe0/PS system, and its degradation products mainly included 6 compounds. There may be two degradation paths: hydroxyl rearrangement and hydroxyl removal in the studied system.