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The molecular structure, rheological properties, microstructure and physical stability of oil-in-water emulsions using octenyl succinic-sugary maize soluble starch (OS-SMSS) were investigated and compared with two commercial OS-starches (HI-CAP 100 and Purity Gum 2000). The degree of substitution (DS), weight-average molecular weight (Mw) and z-root mean square radius of gyration (Rz) of OS-SMSS, HI-CAP 100 and Purity Gum 2000 were 0.0050, 223.4 × 10 5 g/mol and 38.8 nm, 0.0037, 9.6 × 10 5 g/mol and 29.3 nm, and 0.0031, 31.3 × 10 5 g/mol and 39.6 nm, respectively. FT-IR spectra showed two new absorption bands at 1725 and 1570 cm −1 from OS ester linkage in all tested samples. The emulsion with OS-SMSS exhibited a pseudoplastic behavior over the whole shear rate range, whereas other two emulsions showed a similar Newtonian fluid. All hydrophobic starch stabilized emulsions satisfied the Herschel–Bulkley model. All emulsions displayed storage modulus (G′) was higher than loss modulus (G″), and only G′ and G″ of OS-SMSS stabilized emulsion were independent of frequency. The volume-average droplet size ( d 43 ) value of emulsions stabilized by three modified starches was 27.9, 15.2 and 24.4 μm, respectively. During 4 weeks storage, lower change in d 43 of emulsion with OS-SMSS was observed. The above results with schematic models of emulsions suggested that an emulsion with high stability could be prepared using 3% of OS-SMSS due to the formation of high density and thick nanoparticle layer at the interface, indicating OS-SMSS was a Pickering emulsion stabilizer for good long-term stability. [ABSTRACT FROM AUTHOR]