This study aims to research the effects of rosin acid (RA) and size of starch on the properties of Pickering emulsifier. Potato (PS, 10–100 µm), corn (CS, 5–25 µm), and rice (RS, 3–8 µm) starches are modified with RA, and their starch ester is used to prepare Pickering emulsions. The results of scanning electron microscopy, X‐ray diffraction, and nuclear magnetic resonance hydrogen spectrum analysis reveal that the structure of native starch is largely destroyed, and esterification occurs between starch and RA. The starch‐based Pickering emulsion, which is esterified by RA, has the uniform particle size and higher stability than native starch. With prolonged storage, the emulsion of large‐sized RA–starch (PS and CS) show a stable gel phenomenon, and the emulsion of small‐sized RA–starch (RS) is a Newton fluid. In addition, the results indicate that RA–starch displays high viscosity and emulsifying properties.