The emergence of antibiotic agents like sulfamethoxazole (SMX) in soils and surface water can cause serious threat to human and animal health. In this work, mechanisms for the promotive effect of gallic acid (GA) on the transformation of SMX by birnessite were studied. In the absence of GA, the observed pseudo-first-order reaction constants (kobs) decreased as the pH increased from 4.0 to 8.0, in agreement with the decrease in redox potential of birnessite with increasing pH. The changes in chemical state of surface Mn atoms suggested that Mn(IV) played a major role in SMX transformation. SMX was transformed mainly by the bond cleavage of SN and SC, NH oxidation, and self- or cross-coupling reactions, with the formation of seven transformation products. The presence of GA could significantly promote the transformation of SMX, which was more pronounced at pH 6.0 comparing to the effect observed at 4.0. This promotive effect was attributed to both the addition reactions between SMX and GA quinones and the condensation reactions between -COOH of quinones and -NH2 of SMX or its transformation products. Moreover, the addition reaction between SMX and OH coming from the GA oxidation by birnessite was also proposed, while its contribution to SMX transformation was small. Furthermore, pyrogallol and methyl gallate that do not contain electron-withdrawing substituent like -COOH group are less effective in promoting SMX transformation than GA, suggesting the electron-density of β‑carbon is key to the occurrence of addition reaction. Our results demonstrate the important role of birnessite and naturally occurring phenolic acids in abiotic transformation SMX, which will profoundly affect its mobility and bioavailability in environments.