Appropriate levels of volatile aroma compounds are the most important factors influencing the quality of Chinese Baijiu, an alcoholic beverage from China, and the perception of Chinese Baijiu flavor and aroma is the result of a large amount of interactions between a great deal of volatile aroma compounds and sensory receptors. During fermentation of Chinese Baijiu, most of the volatile aroma compounds are owing to the metabolic activity of microbial community. Yeast, one of the most important microorganisms, plays an important role in formation of higher alcohols, esters and many other aroma compounds. Meanwhile, many environmental factors greatly affect the production of volatile aroma compounds, of which yeast-derived aroma compounds are affected by factors acting on the expression of relevant yeast genes. The known function and regulation of several individual genes are involved in volatile aroma metabolism of Saccharomyces cerevisiae. ATF1 and ATF2 genes code for alcohol O-acetyltransferases, key enzymes for the synthesis of acetate esters from higher alcohols. EHT1- and EEB1-encoded esterases are required for synthesis of the medium-chain volatile flavor esters. Isoamyl acetate is degraded into a higher alcohol by the catalysis of IAH1-encoded esterase. BAT2 gene codes for a cytosolic branched-chain amino acid aminotransferase which plays an important role in the synthesis of branched-chain alcohols. LEU1-, LEU2-, and ILV1-encoded enzymes affect the production of higher alcohols in Harris pathway. Different environmental factors effect on the expression of these gene to have a large impact of volatile aroma production. Furthermore, in fermentation process of Chinese Baijiu, material, composition of distillers' grains, temperature and oxygen have great influences on the quality of base liquor.