The physicochemical properties of cassava residues subjected to microwave (or steam)-heated acid pretreatment (MHAP or SHAP) were comparatively investigated to improve fermentative hydrogen and methane cogeneration. The hydrogen yield from cassava residues with MHAP and enzymolysis was higher (106.2 mL/g TVS) than that with SHAP and enzymolysis (102.1 mL/g TVS), whereas the subsequent methane yields showed opposite results (75.4 and 93.2 mL/g TVS). Total energy conversion efficiency increased to 24.7%. Scanning electron microscopy images revealed MHAP generated numerous regular micropores (similar to 6 mu m) and SHAP generated irregular fragments (similar to 23 mu m) in the destroyed lignocellulose matrix. Transmission electron microscopy images showed SHAP generated wider cracks (similar to 0.2 mu m) in delaminated cell walls than MHAP (similar to 0.1 mu m). X-ray diffraction patterns indicated MHAP caused a higher crystallinity index (33.00) than SHAP (25.88), due to the deconstruction of amorphous cellulose. Fourier transform infrared spectroscopy indicated MHAP caused a higher crystallinity coefficient (1.20) than SHAP (1.12). (C) 2014 Elsevier Ltd. All rights reserved.