In an aquatic ecosystem, especially constructed wetlands receiving arsenic (As)-containing wastewater, the fate and mobility of As is influenced by manganese (Mn) oxides and organic matter. Although Mn oxides have been extensively investigated for As(V) adsorption, effects of low molecular weight organic acids (LMWOAs) with different functional groups on As(V) adsorption onto birnessite and underlying mechanisms remain elusive. In this study, LMWOAs with two carboxyl groups (including tartaric (TA), malate (MA), and succinic acids (SA) with two, one and zero hydroxyl groups, respectively) were used. Results showed that more As(V) was adsorbed on birnessite with the presence of LMWOA, indicating that the LMWOA promoted As(V) adsorption via birnessite-carboxyl-As(V) ternary complex. Before birnessite dissolution, TA and MA facilitated As(V) adsorption more efficiently than SA, indicating that hydroxyl group enhanced the coordination among carboxyl groups, As(V) and birnessite. However, within high TA/MA batches, As(V) concentrations decreased sharply and then gradually increased, but Mn(II) concentrations continuously increased, showing the initial reductive dissolution of birnessite promoted As adsorption, while further dissolution was conducive to As mobilization. This study identifies the mechanisms of As adsorption in the presence of LMWOAs and highlights the importance of functional groups in As fate and mobility in aqueous environments.