In this study thermoplastic starch (TPS) was prepared with four different molecular weight polyol plasticizers: glycerol, sorbitol, diglycerol and polyglycerol. Diglycerol-TPS (DTPS) and polyglycerol-TPS (PTPS) show significantly lower moisture uptake and a higher temperature stability when compared to conventional glycerol-TPS (GTPS). TPS formulations were blended with HDPE at a concentration of 20 TPS/80 HDPE wt% and a range of interfacial modifier contents via a one-step extrusion process. The emulsification curves of the blends, which track the volume and number average diameter of the dispersed TPS domains with per cent interfacial modifier, show significantly different profiles and a non-correspondence between the d(n) and d(v) values at the critical concentration for interfacial saturation. The addition of small amounts of interfacial modifier to the blends prepared with diglycerol and polyglycerol results in TPS dispersed phases of wide polydispersity with droplets in the order of 200-300 nm coexisting with droplets of 5-7 mu m. This wide polydispersity of TPS phase size can give insight into the mechanism of droplet formation in these systems with interfacial modifier and is indicative of an erosion-type mechanism, where small portions of the TPS droplet break off at the outer part of the droplet. Blends prepared with GTPS and sorbitol-TPS do not display this behaviour and show a more classic correspondence of d(n) and d(v) at the critical concentration. Dynamic mechanical analysis shows miscible behaviour for DTPS and PTPS and partially miscible behaviour for GTPS. This phenomenon was attributed to the presence of ether bonds in the chemical structure of diglycerol and polyglycerol. The increased chain flexibility and lower cohesive energy forces of diglycerol and polyglycerol lead to a more homogeneous TPS phase and consequently an erosion-type compatibilization at the interface. The mechanical properties of blends prepared with polyglycerol and diglycerol show a similar overall behaviour to glycerol.