The formation of bromate by ozone–vacuum ultraviolet (VUV) (185+254 nm) process in comparison with ozone and ozone-ultraviolet (UV) (254 nm) processes of coagulated and softened water was studied. The effects of pH (7, 9, and 11), ozone dosage (1, 2, and 4 mg O3/mg C), and VUV power (30, 60, and 120 W) were investigated. Bromate concentrations formed by the ozone-VUV process were up to four and six times less than those by the ozone and ozone-UV processes, respectively. Among the variables studied, ozone dosage had the most effect on bromate formation by the ozone-VUV process. Approximately 64 and 213% increases of bromate concentration were observed when the ozone dosage was increased from 1 to 2 and 4 mg O3/mg C with VUV power of 120 W at pH 7. The bromate formation also increased as VUV power and pH increased. Hydroxyl radical exposure had a positive relationship with ozone dosage and bromate formation. Results further indicated that it might be difficult to achieve the drinking water standard for bromate and high organic matter removal concurrently.