To bring surface hydrophobicity to thermoplastic starch (TPS) materials for food packaging, fatty acid starch esters (FASE), specifically starch tri-laurate, were incorporated into TPS formulations. A total of three different ratios of FASE (2%, 5% and 10%) were added to the TPS formulation to evaluate the influence of FASE onto physico-chemical properties of TPS/FASE blends, i.e., surface hydrophobicity, dynamic vapor sorption (DVS), and tensile behaviors. Blending TPS with FASE leads to more hydrophobic materials, whatever the FASE ratio, with initially measured contact angles ranging from 90° for the 2%-FASE blend to 99° for the 10%-blend. FT-IR study of the material surface and inner core shows that FASE is mainly located at the material surface, justifying the increase of material surface hydrophobicity. Despite this surface hydrophobicity, blending TPS with FASE seems not to affect blend vapor sorption behavior. From a mechanical behavior perspective, the variability of tensile properties of starch-based materials with humidity rate is slightly reduced with increasing FASE ratio (a decrease of maximal stress of 10-30% was observed for FASE ratio 2% and 10%), leading to more ductile materials.