Prolamins are a group of safe food additives that are biocompatible, biodegradable, and sustainable. Zein, gliadin, kafirin, and hordein are common prolamins that have been extensively studied, particularly as these form colloidal particles because of their amphiphilic properties. Prolamin‐based binary/ternary complexes, which have stable physicochemical properties and superior functionality, are formed by combining prolamins with polysaccharides, polyphenols, water‐soluble proteins, and surfactants. Although the combination of prolamins with other components has received attention, the relationship between the structural design of prolamin‐based complexes and their functionalities remains uncertain. This review discusses the production methods of prolamin‐based complexes, the factors influencing their structural characteristics, and their applications in the food industry. Further studies are needed to elucidate the structure–function relationships between prolamins and other biopolymers, as well as the toxicological effects of these complexes in food.