Chemical modification with octenyl succinic anhydride (OSA) helps to control the physicochemical and thermal properties of isolated starches. The main objective, herein, was to partially characterize modified starches from Dominico-Harton plantain and FHIA 21 planted in Colombia. The highest degree of substitution was found in FHIA 21 (0.020) starch with 3% OSA and 4-h reaction at room temperature. The grain morphology was not affected, but small changes on the surface were evident. Both modified starches reported absorption bands in the IR at 1566 and 1738 cm−1, proper for these types of starch derivatives. The hexagonal and monoclinic structures of starch were altered through chemical modification. In the bending curves, a drastic decrease in the viscosity of the modified starches was observed with respect to the native one. The gelatinization temperatures of the modified starches were similar to those of the isolated starches.