(+)-catechin is one category of flavonoids in cocoa shell waste and it has been reported to have many health benefits. In order to isolate it from aqueous extracted solution of cocoa shell waste by solid phase extraction (SPE), a series of dual ionic liquids@ZIF8-covered silica were prepared as the sorbents. Regarding the operation conditions of SPE and the characteristic structure of (+)-catechin, ZIF8-covered silica was synthesized to establish a stable and porous substrate, and various dual ionic liquids with multiple properties were immobilized on substrate to obtain a high adsorption capacity. Different adsorption conditions were investigated and the highest adsorption capacity (58.0 mg/g) was obtained on Sil@ZIF8@EIM-EIM at 30 °C during 60.0 min. When the sorbent was applied in the SPE process, 96.0% of the total amount of (+)-catechin from cocoa shell waste can be isolated after several washing and elution steps. The satisfactory recoveries of 97.5–100.2% and RSDs of 1.3–3.2% revealed that the SPE process was accurate and precise. The stability of Sil@ZIF8@EIM-EIM was tested in water and the reusability was tested using repeated adsorption/desorption process. The results revealed that Sil@ZIF8@EIM-EIM as an efficient sorbent can isolate (+)-catechin from cocoa shell waste.