Compositional, physicochemical, and structural properties of maltodextrins and the most important advances that have been made are critically reviewed. Individual topics focuses on the maltodextrin production, carbohydrate composition, and dextrose equivalent determination, factors that alter the polysaccharide properties, the molecular arrangement, the mechanisms and complex physicochemical changes of maltodextrins such as water interaction (hygroscopicity, precipitation, turbidity, bound and free water) and the role of molecular interactions for a network formation. Of particular importance is the information concerning the network structure of maltodextrins gels (degree of crystallinity, crystallite size, aggregation) and the involvement of linear and branched chains for the network formation. Rheological properties have become a desirable tool to predict and understand their structural and functional properties, in single and in mixed systems with other macromolecules. These advances are assessed together with the structural development of food products and processes. Their main food applications, particular advantages, recent commercial directions, and modifications together with potential problems are also discussed. As food ingredients, maltodextrins are a valuable production tool, but still with considerable promises. Nevertheless, a more detailed knowledge of the properties of maltodextrins is necessary in order for their use to be considered as sufficiently effective and desirable in a number of known food applications and for novel development purposes.