As a demonstration that second-order nonlinear optical microscopy is a powerful tool for rice grain science, we observed second-harmonic generation (SHG) images of amylosefree glutinous rice and amylose-containing nonglutinous rice grains. The images obtained from SHG microscopy and photographs of the iodine-stained starch granules indicate that the distribution of starch types in the embryo-facing endosperm region (EFR) depends on the type of rice and suggests that glucose, maltose, or both are localized on the testa side of the embryo. In the testa side of the embryo, crystallized glucose or maltose are judged to be detected by SHG. These monosaccharides and disaccharides play an important role, as they trigger energy in the initial stage of germination. These results confirm SHG microscopy is a good method to monitor the distribution of such sugars and amylopectin in the embryo and its neighboring regions of rice grains.