Esterification is a normal method for starch modification while reaction condition is not clear. Here, pure corn starch and vinyl acetate were chosen for starch esterification. Reaction conditions involving esterifying agent content, pH, reaction time and temperature were explored. Dess‐Martin periodinane (DMP) pretreatment was adopted to accelerate esterification. Main results reveal that a content of 30 wt% vinyl acetate, pH = 9, time as 1 h and temperature as 45°C is an optimized condition for vinyl acetate esterification and DMP oxidization can enhance it. After modification, variations in microstructure, surface morphology and macroscopic properties such as viscosity, transparency, adhesion property were explored by FT‐IR, XRD, SEM, TGA, UV–Vis, viscosity, and slushing experiments. Main results reveal that after esterification carbonyl groups were introduced, lattice plane occurred expansion, surface morphology was destroyed, water absorption capacity, viscosity, and gelatinization temperature decreased while transparency, thermal‐stability and adhesion property increased. DMP treatment enhanced the previous variations. It seems via a middle‐level DMP pretreatment and vinyl acetate esterification starch solution viscosity and gelatinization temperature decreased greatly while transparency and adhesion force increased greatly, possibly having a potential use in textile industry. For instance, using as slurry its manufacture cost can be decreased with decreased energy consumption, economical.