In this study, starch-polyphenol complexes (CES-TPS complexes) were prepared using various ratios (0%, 2%, 4%, 6%, 8%, and 10%, based on starch) of tea polyphenols (TPS) and high amylose corn starch (HACS) pretreated with starch branching enzyme (SBE). It was aimed to determine the effects of TPS on the physicochemical and structural properties and digestibility of the CES-TPS complexes. Scanning electron microscopy and laser particle size analysis showed that the addition of a moderate amount of TPS will reinforce interaction force, while excessive TPS will cause a loose structural morphology, leading to an increase in starch particle size. Thermal property analysis indicated that SBE pre-treatment decreased TO, TP and TC of HACS, and the gelatinization temperature was further reduced after adding TPS. The digestion of CES-TPS complexes was investigated using an Artificial Gut analyzer; the predicted glycemic index of starch samples decreased with the addition of a low concentration of TPS (2-6%), while there was a significant increment in the pGI of starch samples when a high concentration of TPS (8-10%) was added. XRD analysis showed that the relative crystallinity of the CES-TPS complexes further increased to 21.91% and then decreased to 19.38% with the increase of TPS concentration. The ratios of 1047/1022 cm-1 presented the opposite trend to that determined by FT-IR.