Huangjiu is a traditional Chinese fermented alcoholic beverage made from glutinous rice. The quality and flavor profile of Huangjiu are intricately linked to the intrinsic properties of the rice used. While research on rice for Huangjiu emphasizes macronutrients such as starch and protein, little is known about the characteristics of small molecular metabolites. Here, we characterized the macromolecular profiles of three glutinous rice varieties suitable for Huangjiu brewing, and matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) was applied to map the distribution and relative abundance of small molecular metabolites within the rice grains, providing insights for the development of specialized rice varieties for brewing.