Cassava residues were pretreated by ionic liquid N-methylmorpholine-N-oxide (NMMO). NMMO-pretreated cassava residues generated deep grooves (∼4 μm in width) and pores. Cellulose I became cellulose II in NMMO-pretreated cassava residues. H2 yield from NMMO-pretreated cassava residues after enzymolysis was enhanced. Overall energy conversion increased to 21.4–27.9% in H2/CH4 cogeneration.