Starch blends are a technological alternative aimed at the development of starchy matrices that exhibit improvements in some physicochemical properties from interactions between their individual components. Native cassava and yam starches were mixed in different proportions and the effect of the blend on the structural, physicochemical, and pasting properties was evaluated. The viscosity behavior as a function of temperature revealed a significant non-additive effect on the pasting parameters of all the blends with respect to the individual native starches. Similarly, non-additive variations were evident in the crystallinity index of some mix ratios (NSB-2: 40.11%). Likewise, the difference in the amylose content of each native starch (20.88-25.66%) possibly exerted an effect on the resulting semicrystalline characteristics of the blends and the gelatinization behavior. Hence, the botanical origin and the proportion of starch blends play an important role in the behavior of the resulting physicochemical properties and in vitro digestibility. Polymeric blends were obtained with a low tendency to retrogradation and lower crystallinity index values compared to their native counterparts and a regulated water absorption capacity, all potentially desirable characteristics in the food industry.