Aging process during storage is a key process in improving the quality of Baijiu. Laobaigan base Baijiu as a research project was stored for 156 d with three different methods, natural temperature storage (room temperature), constant temperature storage (40℃) and alternating temperature storage (40℃ for 12h and cooled naturally for 12h every day). Headspace solid-phase microextraction combined with GC-MS and GC-O were used to study the effects of different aging methods on the changes of volatile flavor components in base Baijiu. A total of 55 volatile flavor components was identified, 43 out of these with relatively high contents and Baijiu flavor characteristics were monitored during 156 d storage by external standard quantity, and the changes of odor activity value were calculated then. Results showed that the contents of most esters increased gradually with time at alternative temperature storage, and the contents of most esters increased first and then decreased at constant temperature. The contents of ethyl lactate, ethyl acetate, isoamyl acetate, hexyl acetate, ethyl hexanoate, 3-methylbutyl hexanoate, ethyl 4-methyl valerate, ethyl nonanoate, ethyl undecanoate, ethyl tetradecanoate, ethyl oleate, diethyl succinate, diethyl azelate, ethyl phenylacetate at alternative temperature storage were higher than those at natural temperature or constant temperature storages on the 156th day. However, only the content of ethyl palmitate at constant temperature storages was higher than those of the other two groups on the 156th day. Nineteen compounds with odor activity value greater than 1 were potent odorants, they significantly contributed to the overall aroma of Baijiu. The results also showed that the time of constant temperature treatment should not be too long, or the content of esters would regress. The recommended time for constant temperature storage was 128 days. The alternating temperature storage could increase the content of esters and shortened the aging time to a certain extent. These findings pointed out the direction for process optimization in the productive process of base Baijiu, and laid the foundation for the company to optimize the liquor production design and improve product quality.