N-Methyl morpholine-N-oxide (NMMO) is an environmentally friendly and commercially applied cellulose solvent that is suggested for pretreatment of lignocelluloses to improve biofuel productions. However, the underlying mechanisms of the improvements have been poorly understood yet. In an attempt to investigate the mechanisms, pinewood powder and chips were pretreated with 85% (w/w) NMMO at 120°C for 1–15 h. The pretreatment improved ethanol production yield from 7.2% (g/g) for the untreated wood powder to 68.1–86.1% (g/g) and from 1.7% (g/g) for the untreated wood chips to 12.6–51.2% (g/g) of theoretical yield. Similarly, the biogas yields of untreated wood chips and powder were improved from 21 and 66 (mL/g volatile solids) by 3.5–6.8- and 2.6–3.4-folds, respectively. SEM micrographs indicated major increase in the wood porosity by the pretreatment, which would confirm increase in the water swelling capacity as well as enzyme adsorption. The analysis of X-ray diffraction showed considerable reduction in the cellulose crystallinity by the pretreatment, while FTIR spectroscopy results indicated reduction of lignin on the wood surface by the pretreatment.