The invention discloses an emulsified starch with high degree of substitution and a preparation method thereof. The preparation method of the invention comprises the following steps: firstly, adding starch into water for emulsifying, then preheating for 3-8 hours at the temperature of 50-80 DEG C, modifying with alkenyl succinic anhydrides, neutralizing, filtering, and washing the filter cake; then, degrading and filtering the obtained modified starch, regulating the pH value of the filtered solution to 7.0-8.0, and stirring for 10-60min; enabling the obtained product to flow into anion exchange resin for carrying out component separation, and eluting with 5-10% of neutral salt after separation; and finally, desalting the obtained eluent by a membrane filtration method, concentrating and drying to obtain the emulsified starch with high degree of substitution, wherein the degree of substitution is 0.02-0.1. The emulsified starch obtained by the preparation method of the invention has the characteristics of high degree of substitution, easy control, uniform substitution, good surface activity and the like, can be dissolved in cold water, and has wide application in the field of high added-value food chemical industry.