In the natural environment, arsenic (As) is mainly adsorbed on iron oxide minerals. The release of adsorbed arsenic from iron oxide minerals to the water is the main source of arsenic pollution. Microbes play a crucial role for this process. The purpose of this study was to investigate the effect of the sulfate-reducing bacteria Desulfovibrio vulgaris DP4 on the transformation and mobilization of As. The experimental results show that the released As concentration of the two systems is 0 μmol·L-1 at 0 h. Compared with the control, DP4 promotes the desorption of As(Ⅴ) before the 84 h incubation process. The released As concentration reaches the maximum value of 12.6 μmol·L-1 at 13 h, accounting for~79% of the initial total adsorbed As (16 μmol·L-1). The maximum released As concentration is~8.4 times higher than that of the control (1.5 μmol·L-1). After 84 hours, the concentration of the released As in the DP4 system is lower than the abiotic control, which suggests that the released As is readsorbed on the solid surface. During the incubation process, the As mobility is significantly correlated with Eh. The XRD results show that the crystallinity of the solid samples in the DP4 system decreases by~50%. In general, a lower crystallinity of the adsorbent indicates a higher adsorption capacity. This may be one important reason for the As readsorption after 84 h. In addition, the SEM shows that goethite is agglomerated by DP4 and the EDS results indicate that goethite is partially transformed to an Fe-S mineral. Based on XANES, arsenic-sulfur minerals were not detected in the solid phase, which further confirms the SEM-EDS results, that is, that Fe-S minerals formed in the solid phase, rather than As2S3 (AsS). The released As was readsorbed on the secondary iron mineral, resulting in a lower dissolved As concentration in the DP4 system than in the abiotic control. Furthermore, 19% As(Ⅲ) was detected in the solid phase while dissolved As(Ⅲ) was not determined during the incubation process. The results suggest that sulfate-reducing bacteria may directly reduce adsorbed As(Ⅴ) to As(Ⅲ).