Deep eutectic solvent (DES) has been widely developed and applied in extracting the functional components of teas, however, few studies devoted to revealing the composition differences of tea extracts obtained with DES. The present study aims to study the chemical composition and bioactive differences of Dianhong congou black tea extracts prepared by eight choline chloride (ChCl)-based DES. In addition, D-101 macroporous resin was used to remove DES for bioactivity analysis. High performance liquid chromatography (HPLC) and LC-mass spectrometry (LC-MS) were applied to quantitatively and qualitatively analyze chemical composition differences of DES extracts before and after DES removal. Quantitative results showed that DES4 (composed of ChCl and ethylene glycol) was suitable for extracting catechins (e.g., the extracted level of epicatechin gallate was 8.75 mg/g), theaflavins (theaflavin-3,3′-digallate, 1.59 mg/g), and monosaccharides (glucose, 4.97 mg/g), meanwhile DES5 (composed of ChCl and glycerol) was proved to be effective for extracting free amino acids (with highest level of theanine, 19.72 mg/g). LC-MS based metabolomics results showed that DES2 (ChCl-citric acid), DES3 (ChCl-proline), and DES4 had considerable remaining amounts of flavonoid glycosides, theasinensins, and hydrolysable tannins after DES removal. Although purified DES5 extract contained a comparable amount of these marker compounds to other purified DES extracts, its antioxidant and α-glucosidase inhibitory activities were the lowest among others. Combining results from above, DES4 was proved to be the optimum solvent for extracting functional components of Dianhong congou black tea. The finding provided basis for the application of DES extraction method in tea science.