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This paper is aimed to study the suitability of bio-polymers, including poly-lactic acid (PLLA) and Mater-Bi, for the production of hollow components by rotational molding. In order to reduce the brittleness of PLLA, the material was mixed with two different plasticizers, bis-ethyl-hexyl-phthalate (DEHP) and poly-ethylene-glycol (PEG). The materials were characterized in terms of sinterability. To this purpose, thermomechanical (TMA) analysis was performed at different heating rates, in order to identify the endset temperatures of densification and the onset temperatures of degradation. Results obtained indicated that the materials are characterized by a very fast sintering process, occurring just above the melting temperature, and an adequately high onset of degradation. The difference between the onset of degradation and the endset of sintering, defined as the processing window of the polymer, is sufficiently wide, indicating that the polymers can be efficiently processed by rotational molding. Therefore, a laboratory scale apparatus was used for the production of PLLA and Mater-Bi prototypes. The materials were processed using very similar conditions to those used for LLDPE. The production of void-free samples of uniform wall thickness was considered as an indication of the potentiality of the process for the production of biodegradable containers.