Baijiu is the national liquor of China, which has lasted in China for more than 2000 years. Abundant raw materials, multi-strain co-fermentation, and complex processes make the secrets of baijiu flavor and taste still not fully explored. Acid substances not only have a great influence on the flavor and taste of baijiu, but also have certain functions. Therefore, this paper provides a systematic review for the reported acid substances, especially for their contribution to the flavor and functional quality of baijiu. Based on previous studies, this paper puts forward a conjecture, a suggestion, and a point of view, namely: the conjecture of "whether acid substances can be used as 'key factor' for baijiu quality "; the suggestion of "the focus of research on acid substances in baijiu should be transferred to evaluating their contribution to the taste of baijiu"; and the view of "acid substances are 'regulators' in the fermentation process of baijiu". It is worth thinking about whether acid substances can be used as the key factors of baijiu to be studied and confirmed by practice in the future. It is hoped that the systematic review of acid substances in baijiu in this paper can contribute to further in-depth and systematic research on baijiu by researchers in the future.