In this study, Tartary buckwheat starch was modified to different degrees of substitution (DS) with octenyl succinate anhydride (OS-TBS) in order to explore its potential for stabilizing Pickering nanoemulsions. OS-TBS was prepared by reacting Tartary buckwheat starch with 3, 5 or 7% (w/v) octenyl succinate in an alkaline aqueous solution at pH 8.5. Fourier-transform infrared spectroscopy gave peaks at 1726 cm−1 (C=O) and 1573 cm−1 (RCOO−), indicating the formation of OS-TBS. We further studied the physicochemical properties of the modified starch as well as its emulsification capacity. As the DS with octenyl succinate anhydride increased, the amylose content and gelatinization temperature of the OS-TBS decreased, while its solubility increased. In contrast to the original Tartary buckwheat starch, OS-TBS showed higher surface hydrophobicity, and its particles were more uniform in size and its emulsification stability was better. Higher DS with octenyl succinate led to better emulsification. OS-TBS efficiently stabilized O/W Pickering nanoemulsions and the average particle size of the emulsion was maintained at 300–400 nm for nanodroplets. Taken together, these results suggest that OS-TBS might serve as an excellent stabilizer for nanoscale Pickering emulsions. This study may suggest and expand the use of Tartary buckwheat starch in nanoscale Pickering emulsions in various industrial processes.