Rice has been fermented to enhance its application in some foods. Although various microbes are involved in rice fermentation, their roles in the formation of volatile compounds, which are important to the characteristics of fermented rice, are not clear. In this study, diverse approaches, such as partial least squares-discriminant analysis (PLS-DA), metabolic pathway-based volatile compound formations, and correlation analysis between volatile compounds and microbes were applied to compare metabolic characteristics according to each microbe and determine microbe-specific metabolites in fermented rice inoculated by molds, yeasts, and lactic acid bacteria. Metabolic changes were relatively more activated in fermented rice inoculated by molds compared to other microbes. Volatile compound profiles were significantly changed depending on each microbe as well as the group of microbes. Regarding some metabolic pathways, such as carbohydrates, amino acids, and fatty acids, it could be observed that certain formation pathways of volatile compounds were closely linked with the type of microbes. Also, some volatile compounds were strongly correlated to specific microbes; for example, branched-chain volatiles were closely link to , while had strong relationship with acetic acid in fermented rice. This study can provide an insight into the effects of fermentative microbes on the formation of volatile compounds in rice fermentation.