Waxy maize starch acetates with the same degree of substitution (DS) were produced in aqueous medium with 3% or 20% (w/w) sodium hydroxide. The distribution of acetyl groups on amylopectin was studied by enzymatic hydrolysis in combination with chromatographic techniques. Product prepared with 20% NaOH was more resistant to β-amylase but less resistant to α-amylase and isoamylase, indicating more acetyl groups distributed over the external chains or located closer to the non-reducing end of external chains. Settling volume and viscosity of acetylated starch slurry indicated the product prepared with 20% NaOH swelled more than that prepared with 3% NaOH during acetylation. Considering the structure of waxy maize starch, reaction conditions, crystallinity and thermal properties of the acetylated products, it was proposed that high concentration NaOH could improve the reaction process and acetyl groups were more uniformly distributed in amorphous and crystallinity regions of amylopectin in waxy maize starch.