Selenium (Se) is a contaminant of concern in environments affected by discharges from smelting and coal-burning industries. Experiments have been performed to investigate the phase associations of selenium in contaminated sediments under a range of controlled redox conditions. In this study, Se sediment associations were examined using the BCR sequential extraction technique after stabilisation at different redox states. It was shown that although most of the sediment-bound Se is associated with the operationally-defined "organic/sulfide" fraction, as the measured redox potential of the system is increased, more Se moves into the "exchangeable" and "iron/manganese oxyhydroxide" fractions. In these fractions, contaminants can be expected to be more bioavailable. As the mass of Se absorbed to sediments is typically at least an order of magnitude higher than the mass dissolved in porewaters, significant Se exposure may result from oxidative shifts in Se sediment associations.