Arsenic (As) is reported to be effectively sorbed onto natural organic matter (NOM) via thiol coordination and polyvalent metal cation bridged ternary complexation. However, the extent of sorption via complexation with oxygen-containing functional groups of NOM is poorly understood. By equilibrating arsenite, arsenate, and monothioarsenate with purified model-peat, followed by As K-edge X-ray ... [Show full abstract] absorption spectroscopic analysis, this study shows that complexation with oxygen-containing functional groups can be an additional or alternative mode of As sorption to NOM. The extent of complexation was highest for arsenite, followed by monothioarsenate and arsenate. Complexation was higher at pH 7.0 compared to 4.5 for arsenite and arsenate, and vice versa for monothioarsenate due to partial transformation to arsenite at pH 4.5. Modeling of the As K-edge EXAFS data revealed that As…C interatomic distances were relatively longer in arsenate- (2.83 ± 0.01 Å) and monothioarsenate-treated peat (2.80 ± 0.02 Å) compared to arsenite-treatments (2.73 ± 0.01 Å). This study suggests that arsenite was predominantly complexed with carboxylic groups, while arsenate and monothioarsenate were complexed with alcoholic groups of the peat. This study further implies that in systems, where NOM is the major sorbent, arsenate and monothioarsenate can have higher mobility than arsenite.