The complex dielectric constant of O-acetyl-starches with regioselective and the statistical distribution of substituents at the anhydroglucose unit (AGU) are measured in an extended frequency range from 10 mHz to 2 MHz and in the low temperature range from -120 to 0 degrees C. The experimentally determined relaxation spectra are evaluated with the well-known model function of Havriliak-Negami for relaxation processes. In the case of 2-O-acetyl-starch two significant relaxations are detected which are associated with the orientational motion of the methylolgroup at the AGU and the acetylgroup in position C-2. The activation energies are 48 and 60 kJ/mol, respectively. Owing to that assignment of relaxations at the AGU with acetylation in position C-2 has proved that it is possible to describe further relaxation processes in acetylated amylomaize starch with a statistical substitution pattern. It was found that an additional relaxation process is associated with the dynamics of the acetylgroup at the position C-6 at the AGU and characterized by a lower activation energy of 28 kJ/mol. From the analytical point of view these results of dielectric spectroscopy analysis demonstrate that the mobility of the side groups depend significantly on the position at the AGU and the type of substituent in their frequency and temperature dependence.