Phenolic compounds can form complexes with starch during food processing, which can modulate the release of phenolic compounds in the gastrointestinal tract and regulate the bioaccessibility of phenolic compounds. The starchphenolic complexation is determined by the structure of starch, phenolic compounds, and the food processing conditions. In this review, the complexation between starch and phenolic compounds during (hydro)thermal and nonthermal processing is reviewed. A hypothesis on the complexation kinetics is developed to elucidate the mechanism of complexation between starch and phenolic compounds considering the reaction time and the processing conditions. The subsequent effects of complexation on the physicochemical properties of starch, including gelatinization, retrogradation, and digestion, are critically articulated. Further, the release of phenolic substances and the bioaccessibility of different types of starch-phenolics complexes are discussed. The review emphasizes that the processing-induced structural changes of starch are the major determinant modulating the extent and manner of complexation with phenolic compounds. The controlled release of complexes formed between phenolic compounds and starch in the digestive tracts can modify the functionality of starch-based foods and, thus, can be used for both the modulation of glycemic response and the targeted delivery of phenolic compounds.Ruibin Wang and Ming Li contributed equally to this work and should be regarded as co-first author.