Biodegradation plays an important role in the removal of organic micropollutants (OMPs) during riverbank filtration (RBF) for drinking water production. The ability of ammonia-oxidizing microorganisms (AOM) to remove OMPs has attracted increasing attention. However, the distribution of AOM in RBF and its role in the degradation of OMPs remains unknown. In this study, the behavior of 128 selected OMPs and the distribution of AOM and their roles in the degradation of OMPs in RBF were explored by column and batch experiments simulating the first meter of the riverbank. The results showed that the selected OMPs were effectively removed (82/128 OMPs, >70% removal) primarily by biodegradation and partly by adsorption. Inefficiently removed OMPs tended to have low molecular weights, low log P, and contain secondary amides, secondary sulfonamides, secondary ketimines, and benzyls. In terms of the microbial communities, the relative abundance of AOM increased from 0.1%–0.2% (inlet_-sand) to 5.3%–5.9% (outlet_-sand), which was dominated by ammonia-oxidizing archaea whose relative abundance increased from 23%–72% (inlet_-sand) to 97% (outlet_-sand). Comammox accounted for 23%–64% in the inlet_-sand and 1% in the outlet_-sand. The abundances of AOM amoA genes kept stable in the inlet_-sand of control columns, while decreased by 78% in the treatment columns, suggesting the inhibition effect of allylthiourea (ATU) on AOM. It is observed that AOM played an important role in the degradation of OMPs, where its inhibition led to the corresponding inhibition of 32 OMPs (5/32 were completely suppressed). In particular, OMPs with low molecular weights and containing primary amides, secondary amides, benzyls, and secondary sulfonamides were more likely to be removed by AOM. This study reveals the vital role of AOM in the removal of OMPs, deepens our understanding of the degradation of OMPs in RBF, and offers valuable insights into the physiochemical properties of OMPs and their AOM co-metabolic potential.