Apart from its non-toxicity, biocompatibility and biodegradability, starch has demonstrated eminent functional characteristics, e.g., forming well-defined gels/films, stabilizing emulsions/foams, and thickening/texturizing foods, which make it a promising hydrocolloid for various food purposes. Nonetheless, because of the ever-increasing range of its applications, modification of starch via chemical and physical methods for expanding its capabilities is unavoidable. The probable detrimental impacts of chemical modification on human health have encouraged scientists to develop potent physical approaches for starch modification. In this category, in recent years, starch combination with other molecules (i.e., gums, mucilages, salts, polyphenols) has been an interesting platform for developing modified starches with unique attributes where the characteristics of the fabricated starch could be finely tuned via adjusting the reaction parameters, type of molecules reacting with starch and the concentration of the reactants. The modification of starch characteristics upon its complexation with gums, mucilages, salts, and polyphenols as common ingredients in food formulations is comprehensively overviewed in this study. Besides their potent impact on physicochemical, and techno-functional attributes, starch modification via complexation could also remarkably customize the digestibility of starch and provide new products with less digestibility.