Baijiu, a conventional fermented beverage with thousands history, plays a crucial part in physical health of people and social culture in China. The application of high-throughput screening and confirmation of flavor components in the field of authenticity identification and potential function has attracted more and more attention and interest of researchers. With more attention to health, pesticides residues, phthalates, biogenic amines and other hazardous substances remained in Baijiu have also become the quality parameters concerned by consumers. This review aims to present updated and critical overview on the substances analysis of Baijiu by means of hyphenated chromatographic techniques based on various pretreatment approaches in recent years. Subsequently, the advance and main direction of Baijiu composition analysis were evaluated and prospected.