Abstract: Presented work focuses on some detailed studies on enzymatic polysaccharide esterification. As a substrate a maize starch was used. Carboxylic acids with different aliphatic chains were the acylation agents and the process was carried out at different temperature, solvents and substrate: enzymes ratio. Obtained esters were analyzed according to the degree of substitution, degradation of polymer chains and changes in topography of modified starch granules. Obtained results shows that investigated method may be used for obtaining high substituted starches; however the DS strongly depends on the aliphatic chain of the acid.