In the present work, the effects of graphene (Gr) and graphene oxide (GO) on the CA-modified thermoplastic starch (TPS) through the melt processing were investigated. The results of small-amplitude oscillation shear experiments (SAOS) showed a significant enhancing effect of nanoparticles on the storage moduli at lower frequencies, resulting in much stronger gel-like behavior, with the effect being even greater for the Gr-filled nanocomposites. This outcome could be attributed to the 3D network formed between nanoparticles and/or the positive effect of the nanoparticles on the TPS gel strength through enhancing the molecular interactions. The greater enhancing effect of Gr compared to GO could be attributed to the higher lateral dimension and specific surface area of Gr. The results of structural breakdown experiments of the nanocomposite samples showed that the extent of structural breakdown was greater for TPS-Gr1 rather than TPS-GO1. This suggests that, although the enhancing effect of Gr on the gel structure was higher than that of GO, its mechanical strength was still lower than that of TPS-GO1. In addition, the results of structural recovery experiments exhibited significantly lower recovery rate than not only the TPS/GO sample, but also the TPS sample. Add to this the much lower ultimate structural recovery of TPS/Gr sample compared to the TPS/GO sample. From these results, one may conclude that while the enhancing effect of Gr on the G′ of the nanocomposite samples was largely controlled by percolation of the network system between the nanoparticles, the positive impact of the GO-containing nanocomposites was predominantly controlled by the enhanced interaction and bridging effect of the GO nanoparticle. This might be the reason behind the faster structural recovery of GO-filled nanocomposite sample. These results were consistent with the great enhancements observed in the mechanical and electrical properties upon introducing the nanoparticles.