Understanding the nuanced interplay between plant polyphenols and starch could have significant implications. For example, it could lead to the development of tailor-made starches for specific applications, from bakinag and brewing to pharmaceuticals and bioplastics. In addition, this knowledge could contribute to the formulation of functional foods with lower glycemic indexes or improved nutrient delivery. Variations in the complexes can be attributed to differences in molecular weight, structure, and even the content of the polyphenols. In addition, the unique structural characteristics of starches, such as amylose/amylopectin ratio and crystalline density, also contribute to the observed effects. Processing conditions and methods will always alter the formation of complexes. As the type of starch/polyphenol can have a significant impact on the formation of the complex, the selection of suitable botanical sources of starch/polyphenols has become a focus. Spectroscopy coupled with chemometrics is a convenient and accurate method for rapidly identifying starches/polyphenols and screening for the desired botanical source. Understanding these relationships is crucial for optimizing starch-based systems in various applications, from food technology to pharmaceutical formulations.