AbstractIn this study, the morphology and the mechanical properties of thermoplastic starch (TPS)/linear low‐density polyethylene (LLDPE) blends prepared by one‐step and two‐step extrusion processing conditions were contrasted. In the presence of citric acid (CA), the compatibility of TPS/PE blends were proved to transfer to a high continuous dispersion in one‐step extrusion process by scanning electron microscopy analysis. By increasing the interaction between two phases, the mechanical properties of the blends were markedly improved, even reached the levels of the conventional plastics. The rheological study proved that the viscosity (η) of TPS and TPS/PE blends were both decreasing with increase in the content of CA at the same temperature, which ascribed to the acidity of CA was propitious to fragmentation and dissolution of cornstarch granules, deteriorated the chain entanglement in starch, and weakened the interaction of starch molecules. Both FTIR spectroscopy and thermal properties analysis of TPSs and TPS/PE blends showed that the interactions between starch and plasticizer became stronger in the presence of CA. POLYM. COMPOS. 28:89–97, 2007. © 2007 Society of Plastics Engineers