Toxic organic compounds detected generally in source water could combine with chlorine and contribute significantly to chlorination disinfection by-products (CDBPs). The effects of pH on species distribution of CDBPs and the kinetics of chlorination were investigated using phenol as a model of ionizable toxic organic compounds in the pH range of 6.0-9.0. It was found that five chlorination products including 2-monochlorophenol (2-MCP), 4-monochlorophenol (4-MCP), 2,6-dichlorophenol (2,6-DCP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (TCP) were produced by successive chlorination substitution. MCP (2-MCP and 4-MCP) were the dominant products and phenol partly remained in acid media, while TCP and DCP (2,6-DCP and 2,4-DCP) were the main components in neutral and alkaline media. A steady equilibrium of phenol and its chlorination products was reached in 20-30 min in acid-, neutral- and slightly alkaline media, and was delayed to 60-180 min in alkaline media. The difference in properties between phenols and phenolates, and those between HOCl and ClO(-) should be considered simultaneously in explaining the effects of pH on the chlorination process with the theory of electrophilic substitution. These results show that pH plays an important regulating role in the species distribution of CDBPs and the kinetics of chlorination for ionizable toxic organic compounds in chlorination.