The modification of starch digestibility can be achieved through the formation of complexes with polyphenols. We studied the combined impacts of ultrasound and high-pressure homogenization (UT-HPH) on the structure and in vitro digestibility of rice starch-chlorogenic acid complexes. The development of V-type complexes was supported by our findings, which also showed that synergistic UT-HPH therapy exhibited the highest absorbance value for the complexing index (0.882). Significant alterations in digestibility were also observed in the complexes, with the content of RDS decreasing from 49.27% to 27.06%, the content of slowly SDS increasing from 25.69% to 35.35%, and the percentage of RS increasing from 25.05% to 37.59%. Furthermore, a high positive correlation was found by applying the Pearson correlation coefficient in our research between RS, weight, PSD, and CI. This study presents a sustainable processing approach for utilizing chlorogenic acid in starch-rich food systems.