As one of the most popular traditional spirits in China, baijiu has a unique food matrix with high ethanol concentration and a wealth of aroma compounds. The aroma profile volatilized from the cup that has been widely studied may be different from the aroma that consumers perceived during drinking. It is affected by numerous factors, and saliva is a critical one. This study revealed that ex-vivo saliva had a significant positive or negative influence on ester release in simulated solutions, and proved that the degree of effects was related to the hydrophobicity of the compounds. Moreover, the ethanol concentration of simulated baijiu could alter the effect of saliva on esters. Both the effect intensity and the result would be changed, and the performance of the esters was related to their log P-value. Then we examined the underlying mechanism between saliva components and esters under the effect of diverse ethanol concentrations in simulated baijiu solutions with diverse buffers. The high ethanol concentration of baijiu may make the impact of saliva components on the ester release changeable and different from other food matrices because of the chemical and biological change in this system.