The increasing industrial demand and the search for novel ingredients in food and non-food sectors have driven research efforts toward alternatives to traditional commercial starches, emphasizing sustainability and the valorization of native crops, thereby promoting income generation for small-scale farmers. The extraction of these starches through aqueous methods, employing reductive and/or alkaline agents, can impact their structure and technological properties. These starches exhibit distinct physicochemical, morphological, crystalline, thermal, and nutritional characteristics, influenced by factors such as botanical origin. Although certain limitations may exist in their technological applications, physical, chemical, and/or enzymatic modification methods, or a combination thereof, are employed to enhance these properties for specific uses. These alternative starch sources present potential applications across the food, pharmaceutical, paper, medicinal, and cosmetic industries, underscoring their versatility and unique advantages. Nonetheless, ongoing research is essential to fully explore their composition and potential applications. This review serves as a valuable resource for researchers and professionals interested in sustainable and innovative alternatives to conventional starches.