Starch has been widely explored in food additives such as thickeners, stabilizers, and gelling agents due to its excellent properties. However, the poor dispersion and emulsification of starch limit direct applications. To overcome this challenge, starch is extracted from potatoes and etherified to carboxymethyl starch sodium (CMS) to form a cold water soluble starch, which is prepared as an amphiphilic colloid by esterification with lauric acid using Novozym 435 catalyst. As a result of the new groups introduced and concomitant changes produced in the granule structure, carboxymethyl starch sodium laurate starch (CMS‐LS) typically shows strong emulsifying properties, low surface tension, and good amphiphilic properties. Characterizations by Fourier transform infrared (FTIR), Scanning Electron microscope (SEM), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS) show that CMS‐LS is successfully prepared. The results of water solubility, surface tension, contact angle measurement, and emulsification test indicate that CMS‐LS is an excellent emulsifier, amphiphilic polymer and surfactant. Therefore, CMS‐LS is successfully synthesized and esterified, which can be widely used in food, cosmetics, and biomedicine fields.