An ionic liquid of N-methylmorpholine-N-oxide (NMMO) was used to effectively pretreat cassava residues for the efficient enzymatical hydrolysis and cogeneration of fermentative hydrogen and methane. The reducing sugar yield of enzymolysed cassava residues with NMMO pretreatment improved from 36 to 42 g/100 g cassava residues. Scanning electron microscopy images revealed the formation of deep grooves ( similar to 4 mu m wide) and numerous pores in the cassava residues pretreated with NMMO. X-ray diffraction patterns showed that the crystallinity coefficient of NMMO-pretreated cassava residues decreased from 40 to 34. Fourier transform infrared spectra indicated that crystal cellulose I was partially transformed to amorphous cellulose II in the NMMO-pretreated cassava residues. This transformation resulted in a reduced crystallinity index from 0.85 to 0.77. Hydrogen yield from the enzymolysed cassava residues pretreated with NMMO increased from 92.3 to 126 mL/g TVS, and the sequential methane yield correspondingly increased from 79.4 to 101.6 mL/g TVS. (C) 2017 Elsevier Ltd. All rights reserved.