Abstract: Baijiu is one of the most famous traditional fermented food in China, and its quality depends on the interaction of flavor substances. Among the flavor substances, higher alcohols are one of the important aroma and flavor components in Baijiu. Higher alcohols could enrich the aroma and increase the hierarchy and harmony of Baijiu at moderate amount. However, it not only negatively affect the sensory experience of consumers, but also pose potential risks to human health at high levels. Therefore, clarifying the production mechanism of various higher alcohols in Baijiu is crucial to fine control the content of higher alcohols, maintain the specific proportion of different flavor Baijiu, and ensure the quality and safety of Baijiu. In this review, the production mechanisms of the main higher alcohols in Baijiu, such as isoamyl alcohol, isobutanol, n-propanol, phenylethyl alcohol, etc., were comprehensively summarized, and the control strategies of higher alcohols in Baijiu was discussed, including raw material selection, microbial community regulation, environmental factor control, and production technologies improvement, which provided theoretical reference and practical guidance for the production of Baijiu and scientific drinking. Furthermore, the research direction of Baijiu flavor improvement is prospected in order to promote the sustainable and healthy development of the Baijiu industry.