Selenium (Se) is an important element for assessing the safety of high-level waste disposal. Se is redox-sensitive, and its oxidation state varies from -2 to 6 depending on the redox conditions and pH of the solution. Large quantities of ferrous ions formed in bentonite due to corrosion of carbon steel overpack after the closure of a repository are expected to maintain a reducing environment near the repository. Therefore, the migration behavior of Se in the presence of Fe in bentonite was investigated by electrochemical experiments. Na2SeO3 solution was used as tracer solution. Dry density range of bentonite was from 0.8 to 1.4 × 103kg/m3. Results indicated that Se was strongly retained by the processes such as precipitation reaction with ferrous ions in bentonite. Se K-edge X-ray absorption near-edge structure (XANES) measurements were performed at the BL-11 beamline at SAGA Light Source, and the results revealed that the oxidation state of Se in the bentonite remained Se(IV).