Starch-phenol complexes are of interest due to their potential for health-related functional properties in addition to resistance to enzymic digestion. However, the preparation of such complexes remains a challenge due to the structural features and low solubility of the phenols. The present study sets out a novel protocol to prepare amylose (AM)-polyphenol complexes by forming an AM-lipid complex that incorporates the polyphenol. Three polyphenols (resveratrol, curcumin, and quercetin), which by themselves do not form complexes with AM, were successfully encapsulated by AM through the addition of lauric acid (LA) to form AM-LA-polyphenol complexes. These ternary complexes had a more ordered structure and better functional properties, including antioxidant activity, slower enzymatic digestion, and controlled release of polyphenols, compared with the polyphenols alone or the AM-LA complex. Of the three polyphenols, more curcumin and quercetin were captured through interhelical rather than intrahelical associations. Our study opens up a new way to prepare starch-polyphenol complexes using polyphenols that do not form complexes with AM alone, which will be of great significance for creating novel resistant starches with desirable functionalities.