Humic substances are commonly known disinfection byproduct (DBP) precursors. Tannic acid is one precursor of humic substances in organic degradation, and it occurs ubiquitously in both source water and wastewater. In this study, the biological degradation process was simulated under laboratory conditions, and the characteristics of DBP formation generated from the chlorination of tannic acid samples with different biodegradation times were explored. Twenty-six emerging halogenated DBPs were identified, and the formation pathways of the tannic acid-derived DBPs were tentatively proposed. Moreover, results demonstrated that the profile of the chlorinated DBP formation was significantly different from its brominated counterpart during biodegradation, and a general increasing trend of the ratio of TOBr/TOX or TIIPIS79/(TIIPIS79+TIIPIS35) as biodegradation time increasing was noticeable. The observed trend could be mainly ascribed to the reactive sites of tannic acid shifting from relatively fast to slow sites during biodegradation. In addition, the comparative toxicity of the detected DBPs derived from tannic acid was predicted by using two quantitative structure-activity relationship models established previously. On the basis of both the two toxicity metrics (involving developmental toxicity and growth inhibition potency), the predicted toxicity data indicated that the emerging DBP group trihalo-(di)hydroxycyclopentane-1,3-diones may possess extremely high toxic potencies.