High-amylose maize starch (HAM) is a common source material to make resistant starch with its high content of amylose (>70%). In the current investigation, the self-assembly of amylose in the presence of bioactive tea polyphenols (TPLs) and resulting slow digestion property of starch were explored. The experimental results using a mouse model showed a slow digestion property can be achieved with an extended and moderate glycemic response to HAM starch cocooked with TPLs. Further studies using a dilute aqueous amylose solution (0.1%, w/v) revealed an increased hydrodynamic radius of amylose molecules, indicating that TPLs could bridge them together, leading to increased molecular sizes. On the other hand, the bound TPLs interrupted the normal process of amylose recrystallizaiton evidenced by a decreased viscosity and storage modulus (G') of HAM (5%) gel, a rough surface of the cross-section of HAM film, and decreased short-range orders examined by Fourier transform infrared spectral analysis. Single-step degradation curves in the thermal gravimetric profile demonstrated the existence of a self-assembled amylose-TPL complex, which is mainly formed through hydrogen bonding interaction according to the results of iodine binding and X-ray powder diffraction analysis. Collectively, the amylose-TPL complexation influences the normal self-assembling process of amylose, leading to a low-ordered crystalline structure, which is the basis for TPLs' function in modulating the digestion property of HAM starch to produce a slowly digestible starch material that is beneficial to postprandial glycemic control and related health effects.