V-type starch-polyphenol complexes, known for their improved physicochemical properties compared to native starch, are challenging to form efficiently. In this study, the effects of tannic acid (TA) interaction with native rice starch (NS) on digestion and physicochemical properties were investigated using non-thermal ultrasound treatment (UT). Results showed the highest complexing index for NSTA-UT3 (∼ 0.882) compared to NSTA-PM (∼0.618). NSTA-UT complexes reflected the V6I-type complex having six anhydrous glucose per unit per turn with peaks at 2θ = 7°, 13°, and 20°. The maxima of the absorption for iodine binding were suppressed by the formation of V-type complexes depending on the concentration of TA in the complex. Furthermore, rheology and particle size distributions were also affected by TA introduction under ultrasound, as revealed by SEM. XRD, FT-IR, and TGA analyses confirmed V-type complex formation for NSTA-UT samples, with improved thermal stability and increased short-range ordered structure. Ultrasound-induced addition of TA also decreased the hydrolysis rate and increased resistant starch (RS) concentration. Overall, ultrasound processing promoted the formation of V-type NSTA complexes, suggesting that tannic acid could be utilized for the production of anti-digestion starchy foods in the future.