Health-care liquor is a kind of alcoholic beverage with health properties, which is based on Baijiu or other alcoholic drinks, and supplemented with traditional Chinese medicines. Chinese Jingjiu is one of the representative products of health-care liquor, which is usually made based on light-aroma flavor Xiaoqu Baijiu and supplying with dioscoreae rhizoma, curculiginis rhizoma, angelicae sinensis radix, cistanches herba, lycii fructus, astragali radix, epimedii folium and other medicinal materials through modern extraction and separation technology. In this study, the kinds and contents of the volatile compounds of two base distillate of Chinese Jingjiu were qualitatively analyzed by liquid-liquid extraction combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOF MS). The results indicated that a total of 175 volatile compounds were identified in two base distillate of Chines Jingjiu, and 40 compounds were identified by standard compounds, including 41 alcohols, 53 esters, 25 aldehydes and ketones, 2 acetals, 24 acids, 8 furans, 3 phenolic compounds, 8 lactones, 8 nitrogen-containing compounds, 1 sulfur-containing compound and 2 acid anhydride compounds. Notably, nitrogen-containing and sulfur-containing compounds were firstly identified in Chinese Jingjiu. In conclusion, the combination of liquid-liquid extraction and GC×GC-TOF MS can rapidly and accurately characterize the volatile compounds in base distillate of Chinese Jingjiu. The results could provide reference for the study of important aroma compounds of Chinses Jingjiu.