The study of the viscoelasticity of starch-based materials has mainly focused on concentrated gels and dispersions (≥5% starch). In this work, the viscoelastic behavior of almost water-free TPS at high glycerol contents has been evaluated at 150 °C. G′ decreases as glycerol content increases and the changes are similar at both low and high frequencies. Della Valle and co-workers also studied the behavior of a water-free TPS at 150 °C and found that the decrease of G′ with glycerol content was dependent on frequency ( Della Valle et al., 1998). However, that material was obtained by subjecting the TPS to a separate drying step, a process, which can induce structural changes in the starch. The proportional reduction of G′ as a function of glycerol content observed in this work is similar to that observed in starch gel systems ( Kulicke et al., 1996). Fig. 6a shows that the reduction of the glycerol content from 40 to 33% results in a quasi-linear increment of G′, while the reduction from 33 to 29% glycerol produces a larger variation in G′. In the case of the elastic modulus of polymer composites, percolation theory explains the non-linearity produced by the phase inversion effect at high filler content ( Willett, 1994).