The electrosorption of U(VI) from waste water was carried out by using an activated carbon fiber (ACF) felt electrode in a continuous electrosorption cell. In order to enhance the electrosorption capacity at a lower potential, the ACF was electrochemically modified in an acidic and a basic solution. Pore structure and functional groups of the electrochemically modified ACF were examined, and the effects of the modification conditions were studied for the adsorption of U(VI). Specific surface area of all the ACFs was decreased by this modification. The amount of the acidic functional groups decreased with a basic modification, while the amount increased a lot with an acidic modification. The electrosorption capacity of U(VI) decreased on the acid modified electrode due to the shielding effect of the acidic functional groups. The base modified electrode enhanced the capacity due to a reduction of the acidic functional groups. The electrosorption amount of U(VI) on the base modified electrode at .0.3 V corresponds to that of the as-received ACF electrode at .0.9 V. Such a good adsorption capacity was due to a reduction of the shielding effect and an increase of the hydroxyl ions in the electric double layer on the ACF surface by the application of negative potential.