The formation of hydroxyl radicals from hydrogen peroxide in alkaline solutions and under the conditions of hydrogen peroxide bleaching of pulps was investigated. The results lend support to the generally accepted view that the decomposition of alkaline hydrogen peroxide is catalyzed by redox processes involving transition metal ion species. The formation of hydroxyl radicals by one-electron reduction of hydrogen peroxide in this process is believed to be catalyzed primarily by mononuclear transition metal ion complexes, polynuclear species being far less efficient in this respect. It was found that a certain formation of hydroxyl radicals during alkaline hydrogen peroxide bleaching of pulp may have a beneficial effect on the final brightness. This finding is ascribed to the cleavage of crosslinks in the rigid lignin matrix which facilitates penetration of the bleaching reagent(s). Silicate does not appreciably suppress the formation of hydroxyl radicals in alkaline hydrogen peroxide solution. The stabilizing effect of this additive is probably due to deactivation of finely dispersed colloidal particles of metal hydroxides and hydrated oxides which decompose hydrogen peroxide to give mainly molecular oxygen and water.