As the depletion of petroleum source and environmental concerns been arises, a new polymer defined as biodegradable material had been extensively study in order to replace the synthetic one. Starch is one of natural materials that been used for producing biodegradable materials. Through gelatinization process, native starches were changed into thermoplastic starch (TPS) in the presence of water and EmimOAc as plasticizers at high temperature (90°C). The structure and interaction of starch/water/EmimOAc have been study using differential scanning calorimetry (DSC). DSC analysis is used to analyse the onset temperature (To), the peak temperature (Tp), the melting temperature (Tm) and melting enthalpy (�H) of samples over a wide range of starch/water/EmimOAc contents. Gelatinization peak shift to higher temperature as the value of EmimOAc is increasing. The values of To, Tp and �H are influenced by the hydrogen bonding capacity of plasticizers. Thus, showed that composition of water/EmimOAc is effectively influence the gelatinization process. © 2016 The Authors.