The acid-catalyzed liquefaction of rape straw in methanol using microwave energy was examined. Conversion yield and energy consumption were evaluated to profile the microwave-assisted liquefaction process. Chemical components of the bio-oils from various liquefaction conditions were identified. A higher reaction temperature was found to be beneficial to obtain higher energy consumption efficiency as heated by microwaves. Fourier transform infrared spectroscopy of the bio-oils indicated that hydroxyl groups underwent oxidation with increasing liquefaction temperature and/or prolonged reaction time; methanol esterification of oxidation products was also observed during the liquefaction process. The GC-MS chromatograms indicated that the further decomposition of C5 and C6 sugars resulted in a remarkable reduction of hydroxyl group products and an apparent increase in levulinic ester; furan derivatives and succinic acid derivatives were increased as well. The chemical reactions in liquefaction for the production of bio-oils mainly included decomposition of hemicelluloses, cellulose, and lignin; the oxidation reactions of the hydroxyl groups and methanol esterification were also presented. Comprehensively, a high content of hydroxyl group products was obtained at a moderate liquefaction condition (140 °C/15 min), and a high yield of levulinic ester products was acquired in severe reaction conditions (180 °C/15 min), regardless of energy consumption efficiency.