In this study, the enhanced mineralization of p-fluoronitrobenzene (p-FNB) was achieved in a methane-based hollow-fiber membrane biofilm reactor (CH4-MBfR). A TOC removal of 73.2% was gained in CH4-MBfR with an influent p-FNB loading of 42―84 mg/L·d, while only 40.6% of TOC was removed in the corresponding control biological reactor (BR). Moreover, the reaction rate constant for TOC removal in CH4-MBfR was 2.48 times that of the BR. VFAs was only detected in CH4-MBfR, although oxidation elimination was the first step for p-FNB removal in both systems. Methylococcus and Methylononas were dominant strains in the CH4-MBfR, which may play an important role in converting CH4 to VFAs and then further enhancing the mineralization efficiency of p-FNB.