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The degradation of three micropollutants (i.e., atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET)) was comprehensively investigated in flow-through UV/chlorine reactors. Results showed that the micropollutants degradation fitted well with pseudo-first-order kinetics (R2 > 0.92) with the order of rate constants following SMX > MET > ATZ. The developed steady-state approximation (SSA) model was roughly applicable in flow-through UV/chlorine reactors with the predictions deviated within 44%. UV photolysis here stood as the major degradation pathway for ATZ while the contribution of non-radical processes (UV photolysis and chlorination) to SMX degradation increased as the reactor internal diameter enlarged. The degradation rates were reduced to varying extents with complex water matrices (chloride, bicarbonate and dissolved organic matter (DOM)) where the inhibition from the DOM was most prominent (up to 73.6%). Although reactors with a larger internal diameter resulted in reduced degradation rate constants, the energy requirements were also lowered. The E EO values of micropollutants degradation by UV/chlorine fell mostly within 1.0 kWh m−3 order−1 in deionized water and under different water matrices. The acute toxicity was observed to be higher after UV/chlorine treatment in tap water, but still stayed low in general. This study revealed the different kinetics and mechanisms of micropollutants degradation in flow-through reactors and demonstrated the potential of the UV/chlorine process in terms of low energy consumption and acute toxicity. [Display omitted] • Micropollutants were efficiently degraded in flow-through UV/chlorine reactors. • A steady-state approximation model was developed and found approximately applicable. • Effects of reactor internal diameter and water matrices were investigated. • Variations of solution acute toxicity during UV/chlorine treatment were evaluated. [ABSTRACT FROM AUTHOR]