Objective To enhance the quality and market value of original bottled Maotai-flavored Baijiu, this study investigates the effects of microwave irradiation on major flavor compounds during the aging process and optimizes the microwave-assisted aging process.Methods Maotai-flavored Baijiu samples were subjected to microwave irradiation, and the effects of irradiation time, irradiation temperature, and power density on the contents of key flavor compounds, including ethyl acetate, ethyl lactate, ethyl butyrate, ethyl hexanoate, acetic acid, and acetaldehyde, were examined in samples stored for 28 days after treatment.Results With increasing irradiation time, ester contents first increased and then fluctuated and decreased, while acetic acid and acetaldehyde contents first increased, then decreased, and increased again. As the irradiation temperature increased, ester and acetic acid contents first increased, then slightly decreased, and finally reached a new peak, whereas acetaldehyde content first increased and then fluctuated and decreased. With increasing power density, the contents of esters, acetic acid, and acetaldehyde all first increased and then decreased. According to the results, under the optimal microwave conditions of 45 min irradiation time, 50 ℃ irradiation temperature, and 1.0 W/mL power density, ethyl acetate, ethyl lactate, ethyl butyrate, ethyl hexanoate, and acetic acid increased by 10.1%, 10.0%, 8.6%, 7.9%, and 9.7%, respectively, compared with untreated samples.Conclusion Under the optimized process parameters, microwave irradiation promotes the formation of esters and acids, thereby accelerating the aging process of Maotai-flavored Baijiu.