Integrated hydroxyl radicals and hot water pretreatment (IHRHW) was employed in the bioconversion of the brown macroalgae Macrocystis pyrifera (M. pyrifera) in this study. The optimum experimental pretreatment condition (100 degrees C, 30 min, 11.9 mM FeSO4) and the predicted optimum pretreatment condition (113.95 degrees C, 29.1 min, 12.75 mM FeSO4) were identified using a central composite design method. All glucan and xylan were recovered as monosaccharides or polysaccharides without a fermentation inhibitor (e.g., hydroxymethyl furfural and furfural). The IHRHW-treated macroalgae digestibility reached 88.1% under the optimum experimental condition, whereas that under the predicted optimum condition reached 92.1%. The value was approximately threefold higher than those obtained with untreated M. pyrifera. Carbohydrate recovery and enzymatic hydrolysis can be significantly enhanced by the new economic hydroxyl radicals and hot water pretreatment. (C) 2014 Elsevier Ltd. All rights reserved.