Saturated fatty acids with different chain lengths, namely lauric acid (LA), myristic acid (MA), palmitic acid (PA), and stearic acid (SA) were complexed with rice starch using ultra-high pressure (UHP, 400, or 500MPa) or heat gelatinization. The microstructure and emulsifying properties of the resulting starch-lipid complexes were analyzed. Compared with controls (starch treated without fatty acid), complexation with fatty acids increased the hydrophobicity of the starch, decreased its average particle size, significantly improved its viscoelasticity and decreased its gelatinization temperature. The emulsion indices of the starch-lipid complexes were determined. Addition of MA treated at 400MPa (400MPa-MA) significantly improved the emulsifying capacity of the starch for Pickering emulsions, the relative occluded volume (ROV) reaching 91.22%, markedly higher than the other complexes. The particle size of 400MPa-MA was significantly smaller than that of the other complexes; the D [4, 3] particle size was 5.08 μm and the contact angle was 65.18°. Light microscopy showed that the Pickering emulsion stabilized with 400MPa-MA had a dense network structure, which was more stable than those of the other complexes. The formation and physicochemical properties of starch-lipid complexes appear to be closely related to the preparation method, and ultra-high pressure treatment appears to be an effective approach to prepare starch-lipid complexes for the stabilization of Pickering emulsions.