Chemical modification of potato starch with citronellyl methacrylate monomer, characterization of obtained materials and its physicochemical properties have been presented. The chemical modification of potato starch under the grafting process with citronellyl methacrylate led to the preparation of novel, amphiphilic materials where from 0.3 to ca. 1.6 hydroxyl groups per glycoside unit were replaced by poly(citronellyl methacrylate) chains. The grafting of poly(citronellyl methacrylate) chains onto starch backbone caused considerably changes in the morphology, polarity, solubility, chemical stability, moisture absorbance, gelatinization properties, thermal stability and decomposition mechanism of the prepared copolymers as compared to native potato starch. The influence of the grafting percent on the above mentioned properties as well as on the pyrolysis mechanism was discussed in detail.