Under photoinhibitory illumination of spinach PSII membranes, the oxygen-evolving complex subunits, OEC33, 24 and 18, were released from PSII. The liberated OEC33 and also OEC24 to a lesser extent were subsequently damaged and then exhibited smeared bands in SDS/urea-PAGE. Once deteriorated, OEC33 could not bind to PSII. The effects of scavengers and chelating reagents on the damage indicated that hydroxyl radicals generated from superoxide in the presence of metal ions were responsible for the damage. These results suggest that, like the D1 protein of the PSII reaction center complex, OEC subunits suffer oxidative damage and turnover under illumination.