The Ethiopian potato (Plectranthus edulis) is an annual tuber crop indigenous to Ethiopia. The crop is underutilized and not much studied despite its high yield of starch, which has a good potential to contribute to the effort in meeting the quickly growing demand for starch. In this study, the effects of the ecotype and isolation methods on the physicochemical, functional, structural, and crystalline properties of starches were evaluated. Starches were isolated from two Ethiopian potato ecotypes (Loffo and Chanqua) using distilled water (DW), 0.01% sodium metabisulphite (SMS), and 1M sodium chloride (NaCl) in the isolation media. The results showed that the lowest starch yield was obtained from Chanqua using DW (97.4%), while the maximum was from Loffo using SMS (99.3%). The L* (lightness) and whiteness values of the starches obtained from Loffo were higher than those of Chanqua starches, with NaCl and SMS extractants yielding the highest values. The bulk density, water activity (aw), pH, proximate composition (moisture content, protein, ash, fat, crude fiber, and carbohydrate contents), and techno-functional properties were established. The majority of these parameters varied depending on both the isolation method and the ecotype. The crystallinity pattern of all starches showed B-type diffraction, with differences in diffraction peak intensities between all starches. FTIR tests showed structural changes as a function of the ecotype and isolation procedure used. The Loffo ecotype exhibited considerably better results, and the SMS isolation method was found to be the most effective way to acquire the highest starch quality in most of the characteristics evaluated.