Dissolved organic matter (DOM) has been identified as precursor for disinfection by-product (DBPs) formation during chlorination. Recently, it has been demonstrated that the characteristics of DOM influence the DBPs formation mechanism. A study was, therefore, initiated to investigate the effects of DOM fractions on DBPs formation mechanism. In the chlorination process, organic acids are dominant precursors of total thihalomethanes (TTHM) because of the νC-O and unsaturated structures. Furthermore, the TTHM formation of organic acids was affected by pH more greatly. Based on the fluorescence spectroscopy analysis, DOM fractions contained several fluorescence substances. During chlorination, humic acid-like substances were found to exhibit high chlorine reactivity and hydrophobic organics decomposed to smaller molecules faster than hydrophilic organics even at lower chlorine dosages. Unlike hydrophobic fractions, hydrophilic organics showed no toxicity following chlorination, suggesting that the toxic structures in hydrophilic organics showed high chlorine reactivity during chlorination.