In the Aqueous Self-Cooled Blanket (ASCB) concept, an aqueous 6Li solution in a metallic structure is used as a fusion reactor shielding-breeding blanket. Radiolysis effects could be very important for the design and the use of an ASCB. Although many aspects of the radiation chemistry of water and dilute aqueous solutions are now reasonably well understood, it is not possible to predict the radiochemical behaviour of the concentrated candidate ASCB solutions quantitatively. However, by means of a worst case calculation for a possible ASCB for the Next European Torus (NET) it is shown that even with an important rate of water decomposition the ASCB concept is still workable. Gas bubbles and explosive mixtures can be avoided by increasing the pressure in the neutron irradiated zone and by extracting and/or recombining the radiolytically produced hydrogen and oxygen. This could require an additional inert gas loop, which could also be used as part of the tritium extraction installation.