Dissolved organic matter (DOM) in MBR-treated municipal wastewater intended for reuse was fractionated through ultrafiltration and XAD-8 resin adsorption and characterized by fluorescence spectroscopy. To probe the influences of DOM characteristics on trihalomethanes (THMs) formation reactivity during chlorination, THMs yield and speciation of DOM fractions was investigated. It was found that chlorine reactivity of DOM decreased with the decrease of molecular weight (MW), and MW > 30 kDa fractions produced over 55% of total THMs in chlorinated MBR effluent. Hydrophobic organics had much higher THMs formation reactivity than hydrophilic substances. Particularly, hydrophobic acids exhibited the highest chlorine reactivity and contributed up to 71% of total THMs formation. Meanwhile, low-MW and hydrophilic DOM were susceptible to produce bromine-containing THMs. Of the fluorescent DOM in MBR effluent, aromatic moieties and humic acid-like had higher chlorine reactivity. Conclusively, macromolecular and hydrophobic organics containing aromatic moieties and humic acid-like must be removed to reduce THMs formation. (C) 2014 Elsevier Ltd. All rights reserved.