AbstractThis work aims at preparing bioderived polymer films by blending poly(lactic) acid (PLA) and poly(dodecylene 2,5‐furandicarboxylate) (PDoF) and containing reduced graphene oxide (rGO) as a multifunctional filler in variable weight fraction (from 0.25 to 2 phr). Although the PLA/PDoF blend results as immiscible, the addition of rGO leads to smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and to a better PLA/PDoF interfacial adhesion, which suggests that rGO may act as a blend compatibilizer. Dynamic mechanical thermal analysis (DMTA) shows that rGO shifts the glass transition of PDoF (≈5°C) to higher temperatures. The addition of 10 wt% PDoF in PLA increases the strain at break (+145%), and the addition of 0.25 phr of rGO to this blend increases its tensile strength (+13%), without significantly modifying the strain at break. Finally, rGO strongly decreases the diffusivity and permeability to O2, N2, and CO2 due to an increased diffusion path for gas molecules. These results highlight the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and gas permeation properties of PLA.