The microwave-assisted methanolysis products from lignocellulose were analyzed with gas chromatography/mass spectrometry. Methyl levulinate (ML) and levoglucosenone derived from cellulose and furfural derived from hemicellulose were identified as the dominant compounds in corn stover methanolysis products. Only ML was revealed to accumulate rapidly over time in the methanolysis of cellulose and corn stover. The ML yields ranged from 34.9 to 84.5 mol % depending upon the starting materials varied among glucose, fructose, sucrose, cellulose, and corn stover. As a consequence of microwave dielectric heating, the ML yields from saccharides were increased significantly by 1.2-13.2 times compared to conventional heating. The results indicate that microwave-assisted methanolysis is a promising technology for the utilization of lignocellulosic materials.