Baked adzuki beans are rich in tantalizing odor and nutritional components, such as protein, dietary fiber, vitamin B, and minerals. To analyze the final quality of baked beans, the acrylamide and volatile formation of adzuki beans were investigated under the conditions of microwave baking and drum roasting. The results indicate that the acrylamide formation in baked adzuki beans obeys the exponential growth function during the baking process, where a rapid increase in acrylamide content occurs at a critical temperature and low moisture content. The critical temperature that leads to a sudden increase in acrylamide content is 116.5 °C for the moisture content of 5.6% (w.b.) in microwave baking and 91.6 °C for the moisture content of 6.1% (w.b.) in drum roasting. The microwave-baked adzuki beans had a higher formation of the kinetics of acrylamide than that of drum-roasted beans due to the microwave volumetric heating mode. The acrylamide content in baked adzuki beans had a significant correlation with their color due to the Maillard reaction. A color difference of 11.1 and 3.6 may be introduced to evaluate the starting point of the increase in acrylamide content under microwave baking and drum roasting, respectively. Heating processes, including microwave baking and drum roasting, for adzuki beans generate characteristic volatile compounds such as furan, pyrazine, ketone, alcohols, aldehydes, esters, pyrroles, sulfocompound, phenols, and pyridine. Regarding flavor formation, beans baked via drum roasting showed better flavor quality than microwave-baked beans.